Superhydrophobic and oleophobic coatings with low VOC binder systems

ABSTRACT

Coating compositions for the preparation of superhydrophobic (SH) and/or oleophobic (OP) surfaces that employ low amounts of volatile organic compounds are described. Also described are the resulting coatings/coated surfaces and methods of their preparation. Such coatings/surfaces have a variety of uses, including their ability to prevent or resist water, dirt and/or ice from attaching to a surface.

This application is a continuation of U.S. application Ser. No.13/972,034, now U.S. Pat. No. 9,546,295 which was filed Aug. 21, 2013,which is a continuation of International Application No.PCT/US2012/025982, which was filed Feb. 21, 2012 and which claims thebenefit of U.S. Provisional Application No. 61/445,001, which was filedFeb. 21, 2011, each of which applications is hereby incorporated byreference in its entirety.

BACKGROUND

The superhydrophobic (SH) and superoleophobic surfaces are defined asthose where water or oil droplet contact angles exceed 150°. Such surfahave a variety of uses, including their ability to prevent or resistwater, dirt and/or ice from attaching to a surface. A variety ofhydrophobic and oleophobic surface coating compositions have beendescribed that employ high amounts of volatile organic compounds (VOCs)including those that participate in atmospheric photochemical reactions.Those contrast with the coating compositions described herein thatutilize water and/or VOC-exempt organic solvents that have been found toundergo limited amounts of atmospheric photochemical reactions and loweramounts of photochemically active VOCs.

SUMMARY

This disclosure sets forth coating compositions that employ water-basedbinder systems that have a low VOC content and/or low non-exempt VOCcontent, thereby providing a variety of environmental benefits in theirapplication. The coating compositions described herein remainsubstantially hydrophobic/oleophobic even when abraded, and haveincreased durability and/or life span when subjected to normal wear andtear compared to coatings where hydrophobic and/or oleophobic componentsare restricted to the coating's surfaces.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a histogram plotting the amount of abrasion (measured in Tabercycles using a CS 10 wheel and 250 g load) causing a loss ofsuperhydrophobicity for five one-step coatings prepared with variousBAYHYDROL® based binders (see Appendix A).

FIG. 2 is a schematic showing the proposed distribution of secondparticles, (“nano particles” e.g., CAB-O-SIL® TS720) across thethickness of coatings prepared with different BAYHYDROL® based binders.First particles are indicated by “X” and second particles are indicatedby small filled circles or dots. The upper portion of the diagramindicates the accumulation of a substantially amount of submicron (e.g.,second particles treated to be hydrophobic) at the surface, likely dueto the absence of co-solvents. In contrast, coating compositions of thepresent disclosure (e.g., those which incorporate co-solvents) permitthe dispersion submicron particles (e.g., second particles treated to behydrophobic) throughout the coating.

FIG. 3 shows a plot of surface roughness (Ra) as a function of coatingthickness for one-step coating made with BAYHYDROL® 140AQ.

FIG. 4 shows a plot of the amount of abrasion (measured in Taber cycles)required to cause a loss in superhydrophobicity against coatingthickness (i.e., Taber cycle variation with coating thickness) for aone-step coating prepared using BAYHYDROL® 140AQ

FIG. 5 shows a plot of the amount of abrasion (measured in Taber cycles)required to cause a loss in superhydrophobicity against coatingroughness measured as Ra (i.e., Taber cycle variation with increasingsurface roughness) for coatings prepared using BAYHYDROL® 140AQ.

FIG. 6 shows a plot of surface roughness, Ra, as a function of thicknessfor one-step superhydrophobic coating on steel plates treated with aone-step coatings of BAYHYDROL® 140AQ and clear 700T with CAB-O-SIL®TS720 ranging from 11-20%. Within the first approximation, all of thedata with three levels of TS720 (11-20%) fit linearly. Ra values forone-step coating using BAYHYDROL® 140AQ with clear 700T varied from 4-15μm for coating having a thickness ranging from 20-80 μm.

FIG. 7 shows a plot of surface roughness, Rz, as a function of thethickness of one-step superhydrophobic coatings on steel platesdescribed in Example 3 and FIG. 6. R_(z) values vary from 25-65 μm forcoating thickness from 20-80 μm

FIG. 8 shows a plot of the amount of abrasion (measured in Taber cycles)required to cause a loss in superhydrophobicity against coatingthickness (Taber abrasion data represents abrasion durability). Thenumber of abrasion cycles is plotted as a function of thickness forone-step superhydrophobic coating on the steel plates as described inExample 3 and FIG. 6.

FIG. 9 shows a plot of surface roughness, Ra, as a function of thicknessfor coatings prepared with one-step superhydrophobic coatings on steelplates. The coatings were prepared with a combination of BAYHYDROL®140AQ and clear POLANE 700T as a binder, TS720 ranging from 11-20%second particles, and 70% of Tiger Drylac first particle. The R_(a) datashows differing levels of surface roughness variations with increasingcoating thickness, the lowest amount of TS720 (11%) having the leastroughness, whereas higher R_(a) values are noted for 15% and 20% TS720.

FIG. 10 shows the surface roughness, Rz, as a function of coatingthickness for one-step superhydrophobic coating on steel platesdescribed in Example 4 and FIG. 9. Values of Rz, as a function ofthickness follows a trend similar to that noted for R_(a).

FIG. 11 shows a plot of the amount of abrasion (measured in Tabercycles) required to cause a loss in superhydrophobicity against coatingthickness for one-step superhydrophobic coatings on steel platesdescribed in Example 4 and FIG. 9. The data show approximately a linearincrease in Taber cycles increasing with increasing coating thickness.The lowest TS720 content (11%) yields the lowest number of Taberabrasion cycles for loss of superhydrophobicity. For TS720 contents of15 and 20%, the number of Taber cycles to loss of superhydrophobicity issimilar. For a given coating thickness, perhaps 50 μm, 11% TS720 gives aTaber value of about 300-400 as opposed to 800 abrasion cycles for TS720at a content of 15 or 20%.

FIG. 12 shows a plot of surface roughness, Ra, as a function of coatingthickness for one-step superhydrophobic coating on steel plates. Thecoatings were prepared using BAYHYDROL® 140AQ and white POLANE 700T, andTS720 second particles in amounts ranging from 11-20%. Ra values show anapproximately linear increase with increasing thickness for each levelof TS720. The lowest values of Ra were noted for TS720 of 15%, and theRa values for TS720 at 20% showed roughness values that were in betweenthose of 11% and 20% TS720.

FIG. 13 shows a plot of surface roughness, Rz, as a function ofthickness for one-step superhydrophobic coating on steel plates. Thecoatings were prepared using BAYHYDROL® 140AQ and white POLANE 700T andwith TS720 in amounts ranging from 11-20%. Rz values show anapproximately linear increase with increasing coating thickness for eachlevel of TS720. The lowest values of Rz were noted for TS720 of 15%, andthe Rz values for TS720 at 20% showed roughness values that were inbetween the values for compositions with 11% and 20% TS720.

FIG. 14 shows a plot of the amount of abrasion (measured in Tabercycles) required to cause a loss in superhydrophobicity against coatingthickness for one-step superhydrophobic coatings on steel plates. Thecoatings were prepared using BAYHYDROL® 140AQ and white POLANE 700T, andTS720 second particles in amounts ranging from 11-20%.

FIG. 15 shows a plot of surface roughness, Ra, as a function ofthickness for one-step superhydrophobic coating on steel plates. Thecoatings were prepared using BAYHYDROL® 140AQ and white POLANE 700T,TS720 second particles in amounts ranging from 11-20%, and 7% of TigerDrylac first particles.

FIG. 16 shows a plot of surface roughness, Rz, as a function ofthickness for one-step superhydrophobic coatings on steel plates. Thecoatings were prepared using BAYHYDROL® 140AQ and clear 700T, TS720second particles in amounts ranging from 11-20%, and 7% of Tiger Drylacfirst particles.

FIG. 17 shows a plot of the amount of abrasion (measured in Tabercycles) required to cause a loss in superhydrophobicity as a function ofthickness for one-step superhydrophobic coatings on steel plates. Thecoatings were prepared using BAYHYDROL® 140AQ and white 700T as abinder, TS720 second particles in amounts ranging from 11-20%, and 7% ofTiger Drylac first particle.

FIG. 18 shows a plot of the amount of abrasion (measured in Tabercycles) required to cause a loss in superhydrophobicity as a function ofcoating thickness for one-step superhydrophobic coatings on steel platesusing BAYHYDROL® 140AQ and clear POLANE® 700T as a binder, and TS720second particles. Data for 5, 7, and 9% TS720 are included forcomparison.

FIG. 19 shows a plot of the amount of abrasion (measured in Tabercycles) required to cause a loss in superhydrophobicity as a function ofcoating thickness for one-step superhydrophobic coatings on steelplates. The coatings were prepared using BAYHYDROL® 140AQ and with whitePOLANE® 700T as a binder and TS&@) second particles. Data for 5, 7, and9% TS720 are included for comparison.

FIG. 20 shows a plot of the amount of abrasion (measured in Tabercycles) required to cause a loss in superhydrophobicity as a function ofcoating thickness for one-step superhydrophobic coatings on steel platesfor one-step superhydrophobic coatings on steel plates. The coatingswere prepared using BAYHYDROL®140AQ and clear POLANE700T as a binder andTS720 second particles. Data for 11% TS 720 are included for comparison.

FIG. 21 shows a plot of the amount of abrasion (measured in Fabercycles) required to cause a loss in superhydrophobicity as a function ofcoating thickness for one-step superhydrophobic coatings on steel platesThe coatings were prepared using BAYHYDROL® 140AQ and with white POLANE700T as a binder and TS720 second particles. Data for 11% TS720 areincluded for comparison.

FIG. 22 shows a plot of the amount of abrasion (measured in Tabercycles) required to cause a loss in superhydrophobicity as a function ofcoating thickness for one-step superhydrophobic coatings on steelplates. The coatings were prepared using BAYHYDROL® 140AQ in combinationwith either clear or white POLANE® 700T (60:40 v/v) as a binder, with11% (w/w) of CAB-O-SIL TS720 second particles. A portion of each bindersystem received Tiger Drylac first particle at 7% w/w to give foursamples. Results of Taber abrasion testing with a 250 g load and CS10wheels are provided in the plot. Although there is scatter in the data,there are two clear trends. First, the plates coated with compositionswithout first particle have higher abrasion resistance based on theTaber wear data than plates coated with compositions comprising TigerDrylac first particles. Second, for a fixed coating thickness of about50 microns, coatings without first particles are about 2.5× moreabrasion resistant.

FIG. 23 shows a plot of Faber abrasion resistance cycles) plotted as afunction of coating thickness for one-step superhydrophobic coatings onsteel plates prepared as described in Example 22, except that eachcoating composition contained 15% TS720. Data from the four sample typesare plotted, and the trend lines from the data in FIG. 22 are includedfor references.

FIG. 24 shows a plot of Taber abrasion resistance (cycles to loss ofsuperhydrophobicity) plotted a function of coating thickness forone-step superhydrophobic coating on steel plates using BAYHYDROL® 140AQand clear and white 700T with TS720 of 20% (i.e., the coating describedin FIGS. 22 and 23 with 20% TS720). Data from all four compositions arecompared, and trend lines for the data in Example 22 are included forreference.

FIG. 25 shows a plot of Taber abrasion resistance (cycles to loss ofsuperhydrophobicity) plotted as a function of coating thickness forone-step superhydrophobic coating on steel plates using BAYHYDROL® 140AQand with clear and white 700T with TS720 of 11% without first particle.This plot shows that for all being equal, white POLANE 700T providesmore Taber durability than clear 700T. For a coating thickness of 50 μm,Taber resistance for the white 700T are about 1.5× that of clear 700T.

FIG. 26 shows a plot of surface roughness, Ra, as a function ofthickness for one-step superhydrophobic coatings on steel plates. Thecoatings were prepared using BAYHYDROL® 140AQ in combination with clearor white POLANE 700T as a binder, TS720 second particles at 11% (w/w),and Tiger Drylac first particle of 7% as indicated.

FIG. 27 shows a plot of surface roughness, Ra, as a function ofthickness for one-step superhydrophobic coating on steel plates.Coatings were prepared using BAYHYDROL® 140AQ in combination with clearor white POLANE 700T as a binder, and TS720 second particles at 11% w/w.The coating composition contained no first particles.

FIG. 28 shows a plot of surface roughness, Ra, as a function ofthickness for one-step superhydrophobic coating on steel plates. Thecoatings were prepared using BAYHYDROL® 140AQ in combination with eitherclear or white POLANE 700T as a binder, TS720 second particles at 11%(w/w), and Tiger Drylac first particle at 7% w/w.

FIG. 29 shows a plot comparing the abrasion resistance (measured asTaber cycles to loss of superhydrophobicity) plotted against coatingthickness. Coatings were prepared with clear POLANE 700T and secondparticles of M5T at 11%, either with or without 7% of S60 firstparticles. Taber measurements were conducted with a 250-g load and CS10wheels.

FIG. 30 shows a plot comparing the abrasion resistance (measured asTaber cycles to loss of superhydrophobicity) plotted against coatingthickness. Coatings were prepared with clear POLANE 700T and secondparticles of M5T at 11%, either with or without 7% of S60 firstparticles. Taber measurements were conducted with a 500-g load and CS10wheels.

FIG. 31 shows a plot comparing the abrasion resistance (measured asTaber cycles to loss of superhydrophobicity) plotted against coatingthickness. Coatings were prepared with clear POLANE 700T and secondparticles of MST at 11%, either with or without 7% of S60 firstparticles. Taber measurements were conducted with a 1,000-g load andCS10 wheels.

FIG. 32 shows a plot comparing the abrasion resistance (measured asTaber cycles to loss of superhydrophobicity) plotted against coatingthickness. Coatings were prepared with clear POLANE 7007, secondparticles of MST at 11%, either with or without 7% of S60 firstparticles and a coating thickness up to 350 microns. Taber measurementswere conducted with a 1,000-g load and CS10 wheels.

FIG. 33 shows the calculation of Ra (arithmetic mean roughness) and Rz(ten point mean roughness). For Ra analysis a section of standard lengthis sampled from the mean line on the roughness chart. The mean line islaid on a Cartesian coordinate system wherein the mean line runs in thedirection of the x-axis and magnification is the y-axis. The valueobtained with the formula given in the figure is expressed inmicrometers unless stated otherwise. For ten-point mean roughness (Rz) asection of standard length is sampled from the mean line on theroughness chart. The distance between the peaks and valleys of thesampled line is measured in they direction. Then, the average peak isobtained among 5 tallest peaks(Yp), as is the average valley between the5 lowest valleys (Yv). The sum of these two values is expressed inmicrometers, unless stated otherwise.

DETAILED DESCRIPTION

Low VOC Coatings

Compositions for forming hydrophobic and/or oleophobic coatingsdescribed in this disclosure include one-step compositions that employwater-based polyurethanes (or combinations of water based polyurethanes)as a binder in combination with one or more types of second particles.The compositions set forth in this disclosure may optionally include oneor more types of first particles in addition to third particles.

The low VOC coating compositions described herein provide coatings thatdo not lose hydrophobicity and/or oleophobicity when their surface isabraded. As the coatings do not lose hydrophobicity and/or oleophobicitywhen abraded, the coatings permit thickness to be used as the basis toincrease the abrasion resistance and durability.

1 Binders

To reduce the amount of VOC's, particularly non-exempt VOC's, that arereleased from coating compositions used to prepare hydrophobic and/oroleophobic coatings, water-based (also denoted as waterborne) bindersmay be used to prepare coating compositions that result in SH and/or OPcoatings, including water-based polyurethanes (e.g., water-basedpolyurethane dispersions (PUDs), emulsions, and/or suspension).

In addition to low volatile organic compound content, water-basedpolyurethanes permit the formation of hydrophobic and/or oleophobiccoatings that remain substantially hydrophobic and/or oleophobic evenafter substantial surface abrasion. Moreover, water-based polyurethanesoffer mechanical flexibility, size/dimensional stability of the driedand cured coating, and they can resist embrittlement due to heat and/orlight exposure. UV curable versions of water-based polyurethanes (e.g.,PUDs) are also available that avoid the need to heat cure coatings,which is economically and environmentally desirable due to reducedenergy expenditure associated with light cureable coating applicationsrelative to those requiring or whose curing is enhanced by heating.

1.1 Water-Based Polyurethanes as Binders

A wide variety of water-based polyurethanes (polyurethane coatingcompositions comprising more than insubstantial amounts of water as asolvent and/or diluent) may be used to prepare hydrophobic and/oroleophobic coatings described herein. Polyurethanes are polymersconsisting of a chain of organic units joined by urethane (carbamate)linkages. Polyurethane polymers are typically formed throughpolymerization of at least one type of monomer containing at least twoisocyanate functional groups with at least one other monomer containingat least two hydroxyl (alcohol) groups. A catalyst may be employed tospeed the polymerization reaction. Other components may be present inthe polyurethane coating compositions to impart desirable propertiesincluding, but not limited to, surfactants and other additives thatbring about the carbamate forming reaction(s) yielding a coating of thedesired properties in a desired cure time.

In some embodiments, the polyurethane employed in the durable coatingsmay be formed from a polyisocyanate and a mixture of —OH (hydroxyl) andNH (amine) terminated monomers. In such systems the polyisocyanate canbe a trimer or homopolymer of hexamethylene diisocyanate (HDI).

Some solvents compatible with such systems include water, n-butylacetate, toluene, xylene, ethyl benzene, cyclohexanone, isopropylacetate, N-methyl pyrrolidone, and methyl isobutyl ketone and mixturesthereof; although not all of these solvents are VOC-exempt.

A variety of water-based (waterborne) polyurethane compositions may beemployed for the preparation of hydrophobic, SH and/or oleophobicsurfaces may be employed. Among the commercial water-based polyurethanesthat may be employed in the preparation of SH and OP surfaces are thosethat comprise polycarbonate, polyester, polyethers and/or polyacrylicurethanes, and their aliphatic counterparts (aliphatic polyesterurethane resins, aliphatic polycarbonate urethane resins, and/oraliphatic acrylic urethanes. The structures of some examples ofpolyacrylic urethanes, polyester urethanes, and polycarbonate urethanesare provided below.

Polyacrylic urethane where x>1, 30>y>2, and z>1

Polyester urethane where v>1, w>1, x>1, 2>y>30 and z>1

Polycarbonate urethane where x>1 and

In some embodiments, the water-based polyurethanes are selected from oneor more members of the POLANE® (e.g., POLANE® 700T, Sherwin Williams,Cleveland, Ohio), KEM AQUA® (Sherwin-Williams), or the BAYHYDROL® (e.g.,BAYHYDROL 110, 122, 124, A145, and 140AQ) families of polyurethaneemulsion/dispersions. The polyurethane emulsions or PUDs used as bindersto prepare the hydrophobic and/or oleophobic coatings described hereinmay be prepared in water, or a water containing medium comprising acosolvent that is water miscible (e.g., isopropanol and/or acetone),particularly cosolvents that are VOC-exempt and water miscible (e.g.,acetone).

Water-based polyurethane binders are compatible with, and show goodadhesion to, a wide variety of surfaces. Using water-based polyurethanebinders, superhydrophobic coatings may be formed on many, if not mostsurfaces including, but not limited to, those of various woods, metals,glasses, ceramics, stone, rubbers, fabrics, and plastics.

In some embodiments, the coating compositions for preparing hydrophobicand/or oleophobic coatings contain binder comprising water-basedpolyurethane emulsions or PUDs, such as polyacrylic urethanes orpolyurethane-acrylic enamels. In one embodiment the PUDs employed as abinder are POLANE® compositions (Sherwin Williams), such as POLANE®700T. In other embodiments, compositions for SH and OP coatingpreparation comprising BAYHYDROL® binders are employed for coatingplastics and very flexible substrates. In such an embodiment, flexiblematerials, such as polycarbonate, ABS, PET, polystyrene, PVC andpolyurethane Reaction Injection Molding (RIM) products, can typically becoated using a one (1) component (1K) waterborne coating.

In another embodiment, the coating compositions for preparinghydrophobic and/or oleophobic coatings contain a binder comprisingwater-based polyester-urethane or aliphatic polyester urethanedispersion or emulsion in a water containing medium. In anotherembodiment, the coating compositions for preparing hydrophobic and/oroleophobic coatings contain a binder comprising water-basedpolycarbonate urethane or aliphatic polycarbonate urethane dispersion oremulsion in a water containing medium. In one embodiment, thepolyurethane emulsion or PUD employed as a binder system is a BAYHYDROL®(Bayer Material Sciences), such as BAYHYDROL® 110, 122, 124, A145,140AQ. In some embodiments the polyurethane binders are UV curable suchas BAYHYDROL® UV 2282, UV 2317, UV VP LS 2280, UV VP LS 2317, UV XP2629, UV XP 2687, UV XP 2689, or UV XP 2690. Water-based polyurethanesmay come as a single component ready to apply composition, or as a twoor three part (component) system.

Data for a number of BAYHYDROL® compositions and data for some waterbased polyurethane compositions, such as POLANE®s (e.g., POLANE® 700T)can be obtained from the manufacturers.

In some embodiments, the water-based polyurethane binders comprise apolycarbonate and/or polyester modified waterborne PUD or an acrylicmodified waterborne PUD, any of which may be used alone or incombination. In some embodiments, the water-based polyurethane binderscomprise a BAYHYDROL® or POLANE® (e.g., POLANE® 700T and BAYHYDROL®124), which may be used alone or in combination.

In some embodiments, the coating composition comprises waterbornepolycarbonate and/or polyester modified waterborne PUD in addition to anacrylic modified waterborne PUD. In such embodiments, the ratio of thewaterborne polycarbonate and/or polyester modified waterborne PUD to theacrylic modified waterborne PUD can be about 30:70, 35:65, 40:60, 45:55,50:50, 55:45, 60:40, 65:35, or 70:30 on a weight-to-weight basis of thecommercially available PUDs. In one such embodiment, the polycarbonateand/or polyester modified waterborne PUD is a BAYHYDROL® selected fromBAYHYDROL® 110, 122, 124, A145, 140AQ and the acrylic modifiedwaterborne PUD is a POLANE® such as POLANE® 700T.

In one embodiment, the coating composition for the application ofsuperhydrophobic and/or oleophobic coatings on surfaces comprises: apolyurethane dispersion or suspension comprising one or more of apolyester urethane, a polyacrylic urethane and/or a polycarbonateurethane; from about 5 to about 30% by weight of second particlescomprising one or more siloxanes, and/or one or more alkyl, haloalkyl,fluoroalkyl, or perfluoroalkyl containing moieties; and optionallycomprising up to about 26% by weight of third particles; wherein saidcoating composition comprises less than 0.3 pounds per gallon ofvolatile non-exempt organic compounds; and wherein the superhydrophobiccoating resulting from the application of said composition to a surfaceretains its superhydrophobicity after 150-1,400 Taber abrasion cycles ata 1000 g load for coating thickness range of 25-300 microns, and/or100-2,500 Taber abrasion cycles at a 250 g load, using a CS10 wheel, asjudged by the inability of more than 50% of the water droplets appliedto the area of the coating subjected to said abrasion cycles to remainon the surface when the planar surface is inclined at 3 degrees. In someembodiments, the polyurethane dispersion or suspension comprises apolycarbonate, a polyurethane, and a polyacrylic urethane. Thepolycarbonate urethane and polyacrylic urethane may be present in anyratio including, but not limited to, 90:10, 80:20, 70:30, 60:40, and50:50 (polycarbonate urethane:polyacrylic urethane).

In some embodiments, the above-describe water-borne polyurethane coatingcompositions (e.g., water based polyurethane dispersions or suspensions)comprise at least one polyester urethane, polyacrylic urethane, and/orpolycarbonate urethane composition that when dried and cured produces acoating that has: (a) a modulus at 100% elongation of 1300 psi orgreater, and/or (b) an elongation percent at break of 150% or greater.In other embodiments, such coating compositions comprise: a polyesterurethane and apolyacrylic urethane; a polyester urethane and apolycarbonate urethane; a polyester urethane and a polycarbonateurethane; or polyester urethane, a polyacrylic urethane, and apolycarbonate urethane.

Superhydrophobic and/or oleophobic coatings compositions may be appliedto form coatings having a broad range of thicknesses. In someembodiments, the coatings will have a thickness in a range selected fromabout 10 μm to about 225 μm or about 30 μm to 350 μm. Within this broadrange are embodiments employing coatings of thicknesses that range fromabout 10 μm to about 25 μm, from about 25 μm to about 50 μm, from about50 μm to about 75 μm, from about 75 μm to about 100 μm, from about 100μm to about 125 μm, from about 125 μm to about 150 μm, from about 150 μmto about 175 μm, from about 175 μm to about 200 μm, from about 200 μm toabout 225 μm, from about 15 μm to about 200 μm; from about 20 μm toabout 150 μm; from about 30 μm to about 175 μm; from about 50 μm toabout 200 μm; from about 20 μm to about 100 μm; from about 100 μm toabout 220 μm; from about 220 μm to about 350 μm; from about 15 μm toabout 150 μm; and from about 160 μm to about 350 μm.

2 First Particles

Embodiments of the coatings disclosed herein may comprise particles thatare added to the binder compositions to improve the mechanicalproperties of the coating, e.g., the durability of the hydrophobicand/or oleophobic coatings. A wide variety of such particles, which arealso known as extenders or fillers, may be added to the binders. Thoseparticles are denoted as “first particles” because the coatingsdescribed herein may have one or more additional types of particles.Such first particles that may be employed in the hydrophobic, SH and/orOP coatings described herein include, but are not limited to, particlescomprising: wood (e.g., wood dust), glass, metals (e.g., iron, titanium,nickel, zinc, tin), alloys of metals, metal oxides, metalloid oxides(e.g., silica), plastics (e.g., thermoplastics), carbides, nitrides,borides, spinels, diamond, and fibers (e.g., glass fibers).

Numerous variables may be considered in the selection of firstparticles. These variables include, but are not limited to, the effectthe first particles have on the resulting coatings, their size, theirhardness, their compatibility with the binder, the resistance of thefirst particles to the environment in which the coatings will beemployed, and the environment the first particles must endure in thecoating and/or curing process, including resistance to temperature andsolvent conditions. In addition, if light is used for curing thecoatings, the particle must be resistant to the required light exposureconditions (e.g., resistant to UV light).

In embodiments described herein, first particles have an average size ina range selected from about 1 micron (μm) to about 250 μm. Within suchbroader range, embodiments include ranges of first particles having anaverage size of from about 1 μm to about 5 μm, from about 5 μm to about10 μm, from about 10 μm to about 15 μm, about 15 μm to about 20 μm, fromabout 20 μm to about 25 μm, from about 1 μm to about 25 μm, from about 5μm to about 25 μm, from about 25 μm to about 50 μm, from about 50 μm toabout 75 μm, from about 75 μm to about 100 μm, from about 100 μm toabout 125 μm, from about 125 μm to about 150 μm, from about 150 μm toabout 175 μm, from about 175 μm to about 200 μm, from about 200 μm toabout 225 μm, and from about 225 μm to about 250 μm. Also includedwithin the broader range are embodiments employing particles in rangesfrom about 10 μm to about 100 μm, from about 10 μm to about 200 μm, fromabout 20 μm to about 200 μm, from about 30 μm to about 50 μm, from about30 μm to about 100 μm, from about 30 μm to about 200 μm, from about 30μm to about 225 μm, from about 50 μm to about 100 μm, from about 50 μmto about 200 μm, from about 75 μm to about 150 μm, from about 75 μm toabout 200 μm, from about 100 μm to about 225 μm, from about 100 μm toabout 250 μm, from about 125 μm to about 225 μm, from about 125 μm toabout 250 μm, from about 150 μm to about 200 μm, from about 150 μm toabout 250 μm, from about 175 μm to about 250 μm, and from about 200 μmto about 250 μm.

First particles may be incorporated into binders at various ratiosdepending on the binder composition and the first particle's properties.In some embodiments, the first particles may have a content rangeselected from: about 1% to about 60% or more by weight. Included withinthis broad range are embodiments in which the first particles arepresent, by weight, in ranges from about 2% to about 5%, from about 5%to about 10%, from about 10% to about 15%, from about 15% to about 20%,from about 20% to about 25%, from about 25% to about 30%, from about 30%to about 35%, from about 35% to about 40%, from about 40% to about 45%,from about 45% to about 50%, from about 50% to about 55%, from about 55%to about 60%, and greater than 60%. Also included within this broadrange are embodiments in which the first particles are present, byweight, in ranges from about 4% to about 30%, from about 5% to about25%, from about 5% to about 35%, from about 10% to about 25%, from about10% to about 30%, from about 10% to about 40%, from about 10% to about45%, from about 15% to about 25%, from about 15% to about 35%, fromabout 15% to about 45%, from about 20% to about 30%, from about 20% toabout 35%, from about 20% to about 40%, from about 20% to about 45%,from about 20% to about 55%, from about 25% to about 40%, from about 25%to about 45%, from about 25% to about 55%, from about 30% to about 40%,from about 30% to about 45%, from about 30% to about 55%, from about 30%to about 60%, from about 35% to about 45%, from about 35% to about 50%,from about 35% to about 60%, or from about 40% to about 60% on a weightbasis.

In some embodiments, where the first particles comprise or consist ofglass spheres, the first particles may be present in any of theforegoing ranges or in a range of from about 1% to about 40%, from about3% to about 45%, from about 10% to about 45%, or from about 2% to about15% on a weight basis.

In other embodiments where the first particles are a polyethylene ormodified polyethylene, the particle may be present in a content rangeselected from any of the foregoing ranges, or in a range of: from about3% to about 20%; about 5 to about 20%; from about 3% to about 15%; fromabout 12 to about 20%; or from about 3% to about 10% on a weight basis.

The incorporation of first particles can lead to a surface that istextured due to the presence of the first particles. In suchembodiments, the presence of the first particles results in a surfacetexture that has elevations on the level of the coating formed. Theheight of the elevations due to the presence of the first particles canbe from less than one micron (where the first particle is just below theline of the binder's surface) to a point where the first particles arealmost completely above the level of the binder coating (although theymay still be coated with binder). Thus, the presence of first particlescan result in a textured surface wherein the first particles cause suchelevations in the binder that have maximum heights in a range up tonearly 250 μm. Accordingly, such elevations can be present in rangesfrom about 1 μm to about 5 μm, from about 1 μm to about 10 μm, fromabout 1 μm to about 15 μm, about 1 μm to about 20 μm, from about 1 μm toabout 25 μm, from about 1 μm to about 50 μm, from about 1 μm to about 75μm, from about 1 μm to about 100 μm, from about 1 μm to about 125 μm,from about 1 μm to about 150 μm, from about 1 μm to about 175 μm, fromabout 1 μm to about 200 μm, from about 1 μm to about 225 μm, from about1 μm to about 250 μm, from about 10 μm to about 80 μm, from about 15 toabout 80 μm, from about 20 to about 100 μm, and from about 30 to about70 μm.

The surface texture of coatings may also be assessed using thearithmetical mean roughness (Ra) or the ten point mean roughness (Rz) asa measure of the surface texture. In some embodiments, a coatingdescribed herein has an arithmetical mean roughness (Ra) in a rangeselected from: about 0.2 μm to about 20 μm; about 0.3 μm to about 18 μm;about 0.2 μm to about 8 μm; about 8 μm to about 20 μm; or about 0.5 μmto about 15 μm. In other embodiments, a coating as described herein hasa ten-point mean roughness (Rz) in a range selected from: about 1 μm toabout 90 μm; about 2 μm to about 80 μm; about 3 μm to about 70 μm; about1 μm to about 40 μm; about 40 μm to about 80 μm; about 10 μm to about 65μm; or about 20 μm to about 60 μm.

In some embodiments the compositions described herein, when dried andcured, produce a surface with an arithmetic mean roughness (Ra) greaterthan zero and less than about 30 microns, 20 microns, 16 microns or 10microns. In other embodiments, the surface roughness of a dried andcured coating is from about 1 to about 20 microns; from about 2 to about15 microns, from about 10 to about 20 microns; or from about 10 to about30 microns.

First particles may optionally comprise moieties that make themhydrophobic and/or oleophobic. Where it is desirable to introduce suchmoieties, the particles may be reacted with reagents that covalentlybind moieties that make them hydrophobic and/or oleophobic. In someembodiments, the reagents may be silanizing agents, such as those thatintroduce alkyl, haloalkyl, fluoroalkyl or perfluoroalkyl moieties(functionalities). In some embodiments, the silanizing agents arecompounds of formula (I) (i.e., R_(4-n)Si—X_(n)), and the variousembodiments of compounds of formula (I) described below for thetreatment of second particles. The surface of many types of firstparticles can be activated to react with silanizing agents by varioustreatments including exposure to acids, bases, plasma, and the like,where necessary to achieve functionalization of the particles.

In embodiments described herein, the first particles are not modified byadding functional groups that impart one or more of hydrophobic and/oroleophobic properties to the particles (e.g., properties beyond theproperties inherent to the composition forming the particles). In onesuch embodiment, first particles do not contain covalently bound alkyl,haloalkyl, fluoroalkyl or perfluoroalkyl functionalities (moieties). Inanother such embodiment, the first particles are not treated with asilanizing agent (e.g., a compound of formula (I)).

2.1 Exemplary Sources of First Particles

First particles may be prepared from the diverse materials describedabove. Alternatively, first particles may be purchased from a variety ofsuppliers. Some commercially available first particles that may beemployed in the formation of the hydrophobic and/or oleophobic (HP/OP)coatings described herein include those in the accompanying Table 1.

TABLE 1 First Particles First Particle First Particle First First SizeCrush particle (Filler) Particle Particle Density Range Strength No. IDType Details (g/cc) (μm) Color (psi) Source Location 1 K1 Glass BubblesGPS^(a) 0.125  30-120 White 250 3M ™ St. Paul, MN 2 K15 Glass BubblesGPS^(a) 0.15  30-115 White 300 3M ™ St. Paul, MN 3 S15 Glass BubblesGPS^(a) 0.15  25-95 White 300 3M ™ St. Paul, MN 4 S22 Glass BubblesGPS^(a) 0.22  20-75 White 400 3M ™ St. Paul, MN 5 K20 Glass BubblesGPS^(a) 0.2  20-125 White 500 3M ™ St. Paul, MN 6 K25 Glass BubblesGPS^(a) 0.25  25-105 White 750 3M ™ St. Paul, MN 7 S32 Glass BubblesGPS^(a) 0.32  20-80 White 2000 3M ™ St. Paul, MN 8 S35 Glass BubblesGPS^(a) 0.35  10-85 White 3000 3M ™ St. Paul, MN 9 K37 Glass BubblesGPS^(a) 0.37  20-85 White 3000 3M ™ St. Paul, MN 10 S38 Glass BubblesGPS^(a) 0.38  15-85 White 4000 3M ™ St. Paul, MN 11 S38HS Glass BubblesGPS^(a) 0.38  15-85 White 5500 3M ™ St. Paul, MN 12 K46 Glass BubblesGPS^(a) 0.46  15-80 White 6000 3M ™ St. Paul, MN 13 S60 Glass BubblesGPS^(a) 0.6  15-65 White 10000 3M ™ St. Paul, MN 14 S60/HS Glass BubblesGPS^(a) 0.6  11-60 White 18000 3M ™ St. Paul, MN 15 A16/500 GlassBubbles Floated 0.16  35-135 White 500 3M ™ St. Paul, MN Series   16A20/1000 Glass Bubbles Floated 0.2  30-120 White 1000 3M ™ St. Paul, MNSeries   17 H20/1000 Glass Bubbles Floated 0.2  25-110 White 1000 3M ™St. Paul, MN Series   18 D32/4500 Glass Bubbles Floated 0.32  20-85White 4500 3M ™ St. Paul, MN Series   19 H50/10000 Glass Bubbles Floated0.5  20-60 White 10000 3M ™ St. Paul, MN EPX Series 20 iMK Glass BubblesFloated 0.6 8.6-26.7 White 28000 3M ™ St. Paul, MN Series 21 G-3125Z-Light Spheres ™ CM^(b) 0.7  50-125 Gray 2000 3M ™ St. Paul, MN 22G-3150 Z-Light Spheres ™ CM^(b) 0.7  55-145 Gray 2000 3M ™ St. Paul, MN23 G-3500 Z-Light Spheres ™ CM^(b) 0.7  55-220 Gray 2000 3M ™ St. Paul,MN 24 G-600 Zeeo-spheres ™ CM^(b) 2.3   1-40 Gray >60000 3M ™ St. Paul,MN 25 G-800 Zeeo-spheres ™ CM^(b) 2.2   2-200 Gray >60000 3M ™ St. Paul,MN 26 G-850 Zeeo-spheres ™ CM^(b) 2.1  12-200 Gray >60000 3M ™ St. Paul,MN 27 W-610 Zeeo-spheres ™ CM^(b) 2.4   1-40 White >60000 3M ™ St. Paul,MN 28 SG Extendo-sphere ™ HS^(c) 0.72  30-140 Gray 2500 Sphere OneChattanooga, TN 29 DSG Extendo-sphere ™ HS^(c) 0.72  30-140 Gray 2500Sphere One Chattanooga, TN 30 SGT Extendo-sphere ™ HS^(c) 0.72  30-160Gray 2500 Sphere One Chattanooga. TN 31 TG Extendo-sphere ™ HS^(c) 0.72  8-75 Gray 2500 Sphere One Chattanooga, TN 32 SLG Extendo-sphere ™HS^(c) 0.7  10-149 Off 3000 Sphere One Chattanooga, TN   White 33 SLTExtendo-sphere ™ HS^(c) 0.4  10-90 Off 3000 Sphere One Chattanooga, TNWhite 34 SL-150 Extendo-sphere ™ HS^(c) 0.62 70 Cream 3000 Sphere OneChattanooga, TN 35 SLW-150 Extendo-sphere ™ HS^(c) 0.68   8-80 White3000 Sphere One Chattanooga, TN 36 HAT Extendo-sphere ™ HS^(c) 0.68 10-165 Gray 2500 Sphere One Chattanooga, TN 37 HT-150 Extendo-sphere ™HS^(c) 0.68   8-85 Gray 3000 Sphere One Chattanooga, TN 38 KLS-90Extendo-sphere ™ HS^(c) 0.56   4-05 Light 1200 Sphere One Chattanooga,TN    Gray 39 KLS-125 Extendo-sphere ™ HS^(c) 0.56   4-55 Light 1200Sphere One Chattanooga, TN    Gray 40 KLS-150 Extendo-sphere ™ HS^(c)0.56   4-55 Light 1200 Sphere One Chattanooga, TN    Gray 41 KLS-300Extendo-sphere ™ HS^(c) 0.56   4-55 Light 1200 Sphere One Chattanooga,TN   Gray 42 HA-300 Extendo-sphere ™ HS^(c) 0.68  10-146 Gray 2500Sphere One Chattanooga, TN 43 XIOM 512 Thermo-plastic MPR^(d) 0.96 10-100 White 508 XIOM Corp. West Babylon,   NY 44 XIOM 512Thermo-plastic MPR^(d) 0.96  10-100 Black 508 XIOM Corp. West Babylon,  NY 45 CORVEL Thermo-plastic Nylon 1.09  44-74 Black ROHM & Philadelphia,PA  ™ Black Powder HASS 78-7001 Coating 46 Micro-glass Fibers MMEGF^(e)1.05 16 × 120 White Fibertec Bridgewater, MA 3082 47 Micro-glass FibersMMEGF^(e) 0.53 10 × 150 White Fibertec Bridgewater, MA 9007DSilane-Treated 48 Tiger Polyester crosslinked Drylac with TGIC(triglycidyl Series 49 isocyanurate) ^(a)GPS-general purpose series^(b)ceramic microspheres ^(c)hollow spheres ^(d)modified polyethyleneresins ^(e)microglass milled E-glass filaments

3 Second Particles

The coatings disclosed herein employ second particles (e.g.,nanoparticles), which bear hydrophobic moieties. A variety of secondparticles can be used to prepare the SH and/or OP coatings describedherein. Suitable second particles have a size from about 1 nano meter(nm) to about 25 μm and are capable of binding covalently to one or morechemical moieties (groups or components) that provide the secondparticles, and the coatings into which they are incorporated,hydrophobicity, and when selected to include fluoroalkyl groups,hydrophobivity and oleophobicity.

In some embodiments, the second particles may have an average size in arange selected from: about 1 nm up to about 25 μm or more. Includedwithin this broad range are embodiments in which the second particleshave an average size in a range selected from: about 1 nm to about 10nm, from about 10 nm to about 25 nm, from about 25 nm to about 50 nm,from about 50 nm to about 100 nm, from about 100 nm to about 250 nm,from about 250 nm to about 500 nm, from about 500 nm to about 750 nm,from about 750 nm to about 1 μm, from about 1 μm to about 5 μm, fromabout 5 μm to about 10 μm, from about 10 μm to about 15 μm, from about15 μm to about 20 μm, from about 20 μm to about 25 μm, from 1 nm toabout 100 nm, from about 2 nm to about 200 nm, from about 10 nm to about200 nm, from about 20 nm to about 400 nm, from about 10 nm to about 500nm; from about 40 nm to about 800 nm, from about 100 nm to about 1 μm,from about 200 nm to about 1.5 μm, from about 500 nm to about 2 μm, fromabout 500 nm to about 2.5 μm, from about 1.0 μm to about 10 μm, fromabout 2.0 μm to about 20 μm, from about 2.5 μm to about 25 μm, fromabout 500 nm to about 25 μm, from about 400 nm to about 20 μm, and fromabout 100 nm to about 15 μm, from about 1 nm to about 50 nm, from about1 nm to about 400 nm, from about 1 nm to about 500 nm, from about 2 nmto about 120 nm, from about 5 nm to about 100 nm, from about 5 nm toabout 200 nm; from about 5 nm to about 400 nm; about 10 nm to about 300nm; or about 20 nm to about 400 nm.

In the above-mentioned embodiments, the lower size of second particlesmay be limited to particles greater than about 20 nm, about 25 nm, about30 nm, about 35 nm, about 40 nm, about 45 nm, about 50 nm, or about 60nm; and the upper size of second particles may be limited to particlesless than about 20 μm, about 10 μm, about 5 μm, about 1 μm, about 0.8μm, about 0.6 μm, about 0.5 μm, about 0.4 μm, about 0.3 μm or about 0.2μm. Limitations on the upper and lower size of second particles may beused alone or in combination with any of the above-recited size limitson particle composition, percent composition in the coatings, and thelike.

In some embodiments, the coatings may contain first particles in any ofthe above-mentioned ranges subject to either the proviso that thecoatings do not contain only particles (e.g., first or second particles)with a size of 25 μm or less, or the proviso that the coatings do notcontain more than an insubstantial amount of second particles with asize of 25 μm or less (recognizing that separation processes forparticles greater than 25 μm may ultimately provide an unintended,insubstantial amount of particles that are 25 μm or less).

In other embodiments, first particles have an average size greater than30 μm and less than 250 μm, and coatings comprising those particles donot contain substantial amounts of particles (e.g., first and secondparticles) with a size of 30 μm or less. In yet other embodiments, thecoatings do not contain only particles (e.g., first and secondparticles) with a size of 40 μm or less, or particles with a size of 40μm or less in substantial amounts. And in still other embodiments, thecoatings do not contain only particles (e.g., first and secondparticles) with a size of 50 μm or less, or particles with a size of 50μm or less in substantial amounts.

In other one embodiments, such as where the second particles areprepared by fuming (e.g., fumed silica or fumed zinc oxide), the secondparticles may have an average size in a range selected from about 1 nmto about 50 nm; about 1 nm to about 100 nm; about 1 nm to about 400 nm;about 1 nm to about 500 nm; about 2 nm to about 120 nm; about 5 nm toabout 100 nm; about 5 nm to about 200 nm; about 5 nm to about 400 nm;about 10 nm to about 300 nm; or about 20 nm to about 400 nm.

Second particles having a wide variety of compositions may be employedin the durable SH and/or OP coatings described and employed herein. Insome embodiments the second particles will be particles comprising metaloxides (e.g., aluminum oxides such as alumina, zinc oxides, nickeloxides, zirconium oxides, iron oxides, or titanium dioxides), or oxidesof metalloids (e.g., oxides of B, Si, Sb, Te and Ge) such as a glass,silicates (e.g., fumed silica), aluminosilicates, or particlescomprising combinations thereof. The particles are treated to introduceone or more moieties (e.g., groups or components) that imparthydrophobicity and/or oleophobicity to the particles, either prior toincorporation into the compositions that will be used to apply coatingsor after incorporation into the coatings. In some embodiments, thesecond particles are treated with a silanizing agent, a silane, siloxaneor a silazane, to introduce hydrophobic and/or oleophobic properties tothe particles (in addition to any such properties already possessed bythe particles).

In some embodiments, second particles are silica (silicates), alumina(e.g., Al₂O₃), titanium oxide, or zinc oxide that are treated with oneor more silanizing agents, e.g., compounds of formula I.

In some embodiments, second particles are silica (silicates), alumina(e.g., Al₂O₃), titanium oxide, or zinc oxide, that are treated with asiloxane.

In some embodiments, the second particles are silica (silicates), glass,alumina (e.g., Al₂O₃), a titanium oxide, or zinc oxide, treated with asilanizing agent, a siloxane or a silazane. In some embodiments, thesecond particles may be prepared by fuming (e.g., fumed silica or fumedzinc oxide).

3.1 Some Sources of Second Particles

Second particles such as fumed silica may be purchased from a variety ofsuppliers, including but not limited to Cabot Corp., Billerica, Mass.(e.g., Nanogel TLD201, CAB-O-SIL® TS-720 (silica, pretreated withpolydimethyl-siloxane), and M5 (untreated silica)) and EvonikIndustries, Essen, Germany (e.g., ACEMATT® silica such as untreatedHK400, AEROXIDE® silica, AEROXIDE® TiO₂ titanium dioxide, and AEROXIDE®Alu alumina).

Some commercially available second particles are set forth in Table 1along with their surface treatment by a silanizing agent or polydimentylsiloxane in Table 2.

TABLE 2 Nominal BET Surface Area of Base Produce Surface Level ofProduct Particle Size Product Name Treatment Treatment (m²/g) (nm)Source M-5 None None 200 — Cab-O-Sil Aerosil ® 200 None None 200 12Evonik Aerosil ® 255 None None 255 — Evonik Aerosil ® 300 None None 300 7 Evonik Aerosil ® 380 None None 380  7 Evonik HP-60 None None 200 —Cab-O-Sil PTG None None 200 — Cab-O-Sil H-5 None None 300 — Cab-O-SilHS-5 None None 325 — Cab-O-Sil EH-5 None None 385 — Cab-O-Sil TS-610Dimethyldichlorosilane Intermediate 130 — Cab-O-Sil TS-530Hexamethyldisilazane High 320 — Cab-O-Sil TS-382 OctyltrimethoxysilaneHigh 200 — Cab-O-Sil TS-720 Polydimethylsiloxane High 200 — Cab-O-SilAerosil ® Polydimethylsiloxane — 100 14 Evonik R202 Aerosil ®Hexamethyldisilaze — 125-175 — Evonik R504 (HMDS) and aminosilaneAerosil ® HMDS based on — 220 — Evonik R812S Aerosil ® 300

As purchased, the particles may be untreated (e.g., M5 silica) and maynot posses any HP/OP properties. Such untreated particles can be treatedto covalently attach one or more groups or moieties to the particlesthat give them HP/OP properties, for example, by treatment with thesilanizing agents discussed above.

4 Third Particles

In some embodiments, the coatings disclosed herein employ thirdparticles, which unlike second particles, do not bear hydrophobicmoieties. A variety of third particles, which typically have a size fromabout 1 nm to 5 μm, can be employed in the superhydrophobic and/oroleophobic coatings described herein.

In some embodiments the third particles may have an average size in arange selected from about 1 nm to about 5 μm or more. Included withinthis broad range are embodiments in which the third particles have anaverage size in a range selected from about 1 nm to about 10 nm, fromabout 10 nm to about 25 nm, from about 25 nm to about 50 nm, from about50 nm to about 100 nm, from about 100 nm to about 250 nm, from about 250nm to about 500 nm, from about 500 nm to about 750 nm, from about 750 nmto about 1 μm, from about 0.5 μm to about 4 μm, from about 2 μm to about4 μm, from 1 nm to about 100 nm, from about 1 nm to about 400 nm, fromabout 2 nm to about 120 nm, from about 2 nm to about 200 nm, from about10 nm to about 200 nm, from about 20 nm to about 400 nm, from about 10nm to about 500 nm; from about 40 nm to about 800 nm, from about 100 nmto about 1 μm, from about 200 nm to about 1 μm, from about 200 nm toabout 900 nm, from about 300 nm to about 800 nm; or from about 400 nm toabout 700 nm μm, from about 500 nm to about μm, or from about 500 nm toabout 1 μm.

In the above-mentioned embodiments, the lower size of third particlesmay be limited to particles greater than about 20 nm, about 25 nm, about30 nm, about 35 nm, about 40 nm, about 45 nm, about 50 nm, or about 60nm; and the upper size of third particles may be limited to particlesless than about 5 μm, about 4 μm, about 3 μm, about 1 μm, about 0.8 μm,about 0.6 μm, about 0.5 μm, about 0.4 μm, about 0.3 μm or about 0.2 μm.Third particles having limitations on either or both of their upper andlower sizes may be used alone or in combination with any of theabove-recited first or second particles in the coating compositions.

Third particles having a wide variety of compositions may be employed inthe durable coatings described and employed herein. In some embodimentsthe third particles are particles comprising oxides of metalloids ormetal oxides including, but not limited to, titanium dioxide, ironoxide(s) (e.g., 2Fe₂O₃H₂O or Fe₂O₃), chromium oxide(s). In otherembodiments, the third particles may comprise materials other than metaloxides including, but not limited to, carbon black, zinc chromate (e.g.,3ZnCrO₄.Zn(OH)₂), azurite (Na₇Al6Si₄O₂₄S2), cadmium sulphide(s),lithopone (ZnS mixed with BaSO₄), CaCO₃, kaolin (hydrated aluminiumsilicate), talc (hydrated magnesium silicate), zinc phosphate, zincchromate, zinc molybdate, barium metaborate, or BaSO₄. (See, e.g.,Paints and Pigments, by Michael D. T. Clark revised and editing byHeather Wansbrough following correspondence with Steve Lipsham,available on the World Wide Web atnzic.org.nz/ChemProcesses/polymers/10D.pdf.)

Third particles may be particulate pigments, e.g., carbon black,titanium dioxide, iron oxide(s), zinc chromates, azurite, chromiumoxide(s) cadmium sulphide(s), lithopone, talc (hydrated magnesiumsilicate), BaSO₄ calcium copper silicate, and Cu₂CO₃(OH)₂. Pigmentsserve not only to provide color, but may also enhance coating resistanceto weather, heat, light, or corrosion. Third particles may also bemineral compounds that do not provide staining power or opacity, knownas extenders. Extenders may be used to improve coating applicationcharacteristics, as “flatting agents” to provide flat or semi-glossfinishes, or to prevent settlement of pigments. Some common extendersinclude CaCO₃, talc, barites, kaolin, silica, and mica. See, e.g.,Paints and Pigments, by Michael D. T. Clark.

In one embodiment, third particles comprise titanium dioxide.

Third particles may be present or absent in the coating compositions,and the resulting coatings described herein. When present, they may bepresent in an amount from about 0.01% to about 25%, from about 0.01% toabout 5%, from about 0.1% to about 5%, from about 1% to about 5%, fromabout 0.01% to about 10%, from about 0.1% to about 10%, from about 2% toabout 10%, from about 0.5% to about 25%, from about 5% to about 25%,from about 5% to about 20%, from about 10% to about 20%, from about0.01% to about 8%, from about 8% to about 16%, from about 16% to about24%, or from about 5% to about 15% by weight based on the weight of thecomposition.

5.0 Hydrophobic and Oleophobic Moieties of First and/or Second Particles

As discussed above, both the first and second particles may comprise oneor more independently selected moieties that impart hydrophobic and/oroleophobic properties to the particles and the coatings into which theyare incorporated. As also noted above, such chemical entities may beassociated with the commercially available particles and/or added by wayof treating the particles.

In some embodiments, the second particles will bear one or more alkyl,haloalkyl, fluoroalkyl, and perfluoroalkyl moieties. Such moieties canbe covalently bound directly or indirectly bound to the second particle,such as through one or more intervening silicon or oxygen atoms. Inother embodiments, the second particles will be treated with a siloxane.

In other embodiments, the second particles will bear one or more alkyl,haloalkyl, fluoroalkyl, and perfluoroalkyl moieties of the formulaR_(3-n)Si—, where n is from 1-3, that are directly or indirectly (e.g.,covalently bound) to the second particle, such as through one or moreintervening atoms.

5.1 Silanizing Agents and their Use

A variety of silanizing agents (e.g., compounds of the formulaR_(4-n)Si—X_(n)) can be employed to introduce moieties, e.g., R_(3-n)Si—groups (where n is an integer from 0 to 2), to the first or secondparticles prior to their introduction into the coatings describedherein. Silanizing agents may also be used to introduce such moietiesonto coating surfaces and onto/into particles subsequent to theirintroduction into the coatings, provided the particles are at or closeenough to the surface of the coating for a silanizing agent to reach andreact with those particles. Suitable silanizing agents typically haveboth leaving groups and terminal functionalities. Terminalfunctionalities are groups that are not displaced by reaction of asilanizing agent with, for example, particles such as silica secondparticles (e.g., R groups of compounds of the formula (I)). Leavinggroups are those groups that are displaced from silanizing agents uponreaction to form bonds with the second particles.

Prior to reacting first or second particles with silanizing agents, theparticles may be treated with an agent that will increase the number ofsites available for reaction with the silanizing agent (e.g., SiCl₄,Si(OMe)₄, Si(OEt)₄, SiCl₃CH₃, SiCl₃CH₂SiCl₃, SiCl₃CH₂CH₂SiCl₃,Si(OMe)₃CH₂Si(OMe)₃, Si(OMe)₃CH₂CH₂ Si(OMe)₃, Si(OEt)₃CH₂Si(OEt)₃, orSi(OEt)₃CH₂CH₂ Si(OEt)₃ and the like). Treatment with such agents isconducted, e.g., with a 1% to 5% solution of the agent in a suitablesolvent (e.g., hexane), although higher concentrations may be employed(e.g., about 5% to about 10%). Where agents such as SiCl₄ or Si(OMe)₄are employed to increase the number of sites available for reaction withsilanizing agents, the surface may first be treated with SiCl₄ followedby reaction with water to replace the chlorines with OH groups thatreact effectively with silanizing agents such as those of formula (I).Reaction with silanizing agents is typically conducted using asilanizing agent at in the range of about 1% to about 2% w/v, althoughconcentrations in the range of about 2% to about 5% w/v may also beused. Depending on the reagents employed, the reaction, which often canbe conducted at room temperature, is typically conducted for 1 hour to 6hours, although reaction for as long as 24 hours may be desirable insome instances. Skilled artisans will appreciate that concentrations andreaction times and conditions other than those described above (e.g.,elevated reaction temperatures) also might be able to be used. In oneembodiment, elevated reaction temperatures from about 30, 40, 50, 60,90, 100, or 120 degrees up to the boiling or decomposition point of thesilinizing agent may be employed.

Second particles can be treated with reactive silanes, siloxanes andsilazanes to produce hydrophobic effects in a solvent free reaction. Inone embodiment the silica and silane are combined in a reaction vesselequipped with a high speed mixing blade. The liquid silane is added tothe agitating particles at a ratio of 2 to 1 by weight. In anotherembodiment, the silica is agitated with a dry air (or inert gas) in acyclone reactor while liquid silane is introduced as a fine spray. Themixtures resulting from either process are heated to 200° F. for 4 to 8hours to complete the reaction and drive off residual volatiles.

In some embodiments, silanizing agents are compounds of the formula (I):R_(4-n)Si—X_(n)  (I)

where n is an integer from 1-3;

-   -   each R is independently selected from:        -   (i) alkyl or cycloalkyl group optionally substituted with            one or more fluorine atoms,        -   (ii) C_(1 to 20) alkyl optionally substituted with one or            more independently selected substituents selected from            fluorine atoms and C₆₋₁₄ aryl groups, which aryl groups are            optionally substituted with one or more independently            selected halo, C_(1 to 10) alkyl, C_(1 to 10) haloalkyl,            C_(1 to 10) alkoxy, or C_(1 to 10) haloalkoxy substituents,        -   (iii) C_(6 to 20) alkyl ether optionally substituted with            one or more substituents independently selected from            fluorine and C_(6 to 14) aryl groups, which aryl groups are            optionally substituted with one or more independently            selected halo, C_(1 to 10) alkyl, C_(1 to 10) haloalkyl,            C_(1 to 10) alkoxy, or C_(1 to 10) haloalkoxy substituents,        -   (iv) C_(6 to 14) aryl, optionally substituted with one or            more substituents independently selected from halo or            alkoxy, and haloalkoxy substituents;        -   (v) C_(4 to 20) alkenyl or C_(4 to 20) alkynyl, optionally            substituted with one or more substituents independently            selected from halo, alkoxy, or haloalkoxy; and        -   (vi) —Z—((CF₂)_(q)(CF₃))_(r), wherein Z is a C_(1 to 12)            divalent alkane radical or a C₂₋₁₂ divalent alkene or alkyne            radical, q is an integer from 1 to 12, and r is an integer            from 1-4;    -   each X is an independently selected —H, —Cl, —I, —Br, —OH, —OR²,        —NHR³, or —N(R³)₂ group;    -   each R² is an independently selected C_(1 to 4) alkyl or        haloalkyl group; and    -   each R³ is an independently selected H, C_(1 to 4) alkyl, or        haloalkyl group.

In some embodiments, R is an alkyl or fluoroalkyl group having from 6 to20 carbon atoms.

In other embodiments, R is an alkyl or fluoroalkyl group having from 8to 20 carbon atoms.

In other embodiments, R is an alkyl or fluoroalkyl group having from 10to 20 carbon atoms.

In other embodiments, R is an alkyl or fluoroalkyl group having from 6to 20 carbon atoms and n is 3.

In other embodiments, R is an alkyl or fluoroalkyl group having from 8to 20 carbon atoms and n is 3.

In other embodiments, R is an alkyl or fluoroalkyl group having from 10to 20 carbon atoms and n is 3.

In other embodiments, R has the form —Z—((CF₂)_(q)(CF₃))_(r), wherein Zis a C_(1 to 12) divalent alkane radical or a C_(2 to 12) divalentalkene or alkyne radical, q is an integer from 1 to 12, and r is aninteger from 1 to 4.

In any of the previously mentioned embodiments of compounds of formula(I), the value of n may be varied such that 1, 2 or 3 independentlyselected terminal functionalities are present in compounds of formula(I). Thus, in some embodiments, n is 3. In other embodiments, n is 2,and in still other embodiments, n is 1.

In any of the previously mentioned embodiments of compounds of formula(I), all halogen atoms present in any one or more R groups may befluorine.

In any of the previously mentioned embodiments of compounds of formula(I), X may be independently selected from H, Cl, —OR², —NHR³, —N(R³)₂,or combinations thereof. In other embodiments, X may be selected fromCl, —OR², —NHR³, —N(R³)₂, or combinations thereof. In still otherembodiments, X may be selected from, —Cl, —NHR³, —N(R³)₂ or combinationsthereof.

Any coating described herein may be prepared with one, two, three, fouror more compounds of formula (I) employed alone or in combination tomodify the first or second particles, and/or other components of thecoating. For example, the same or different compounds of formula (I) maybe employed to modify both the first particles and the binder.

The use of silanizing agents of formula (I) to modify first or secondparticles, or any of the other components of the coatings, willintroduce one or more R_(3-n)X_(n)Si— groups (e.g., R₃Si—, R₂X₁Si—, orRX₂Si— groups) where R and X are as defined for a compound of formula(I). The value of n is 0, 1, or 2, due to the displacement of at leastone “X” substituent and formation of at least one bond between aparticle and the Si atom (the bond between the particle and the siliconatom is indicated by a dash “—” (e.g., R₃Si—, R₂X₁Si—, or RX₂Si—groups).

Exemplary reagents that can be employed to prepare first or secondparticles with hydrophobic and/or oleophobic properties includesilanizing agents such as those that are commercially available fromGelest, Inc., Morrisville, Pa. Such silanizing agents include, but arenot limited to, the following compounds, which are identified by theirchemical name followed by the commercial supplier reference number(e.g., their Gelest reference in parentheses):(tridecafluoro-1,1,2,2-tetrahydrooctyl)silane (SIT8173.0);(tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane (SIT8174.0);(tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane (SIT8175.0);(tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane (SIT8176.0);(heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethyl(dimethylamino)silane(SIH5840.5);(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tris(dimethylamino)silane(SIH5841.7); n-octadecyltrimethoxysilane (SIO6645.0);n-octyltriethoxysilane (SIO6715.0); and3,3,4,4,5,5,6,6,6-nonafluorohexyldimethyl(dimethylamino)silane(SIN6597.4).

Another group of reagents that can be employed to prepare first orsecond particles with hydrophobic and/or oleophobic properties includetridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane;(tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane;nonafluorohexyldimethylchlorosilane;(tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane;3,3,4,4,5,5,6,6,6-nonafluorohexyldimethyl(dimethylamino)-silane;nonafluorohexylmethyldichlorosilane; nonafluorohexyltrichlorosilane;nonafluorohexyltriethoxysilane; and nonafluorohexyltrimethoxysilane. Inone embodiment, the coating compositions set forth herein comprisesilica second particles treated with nonafluorohexyltrichlorosilane.

Two attributes of silanizing agents that may be considered for thepurposes of their reaction with first or second particles and theintroduction of hydrophobic or oleophobic moieties are the leaving group(e.g., X groups of compounds of the formula (I)) and the terminalfunctionality (e.g., R groups of compounds of the formula (I)). Asilanizing agent's leaving group(s) can determine the reactivity of theagent with the first or second particle(s) or other components of thecoating if applied after a coating has been applied. Where the first orsecond particles are a silicate (e.g., fumed silica) the leaving groupcan be displaced to form Si—O—Si bonds. Leaving group effectiveness isranked in the decreasing order as chloro>methoxy>hydro (H)>ethoxy(measured as trichloro>trimethoxy>trihydro>triethoxy). This ranking ofthe leaving groups is consistent with their bond dissociation energy.The terminal functionality determines the level of hydrophobicity thatresults from application of the silane to the surface.

In addition to the silanizing agents recited above, a variety of othersilanizing agents can be used to alter the properties of first or secondparticles and to provide hydrophobic and/or oleophobic properties. Insome embodiments, second particles may be treated with an agent selectedfrom dimethyldichlorosilane, hexamethyldisilazane,octyltrimethoxysilane, polydimethylsiloxane, ortridecafluoro-1,1,2,2-tetrahydrooctyl trichlorosilane. In suchembodiments, the second particles may be silica. Silica second particlestreated with such agents may have an average size in a range selectedfrom about 1 nm to about 50 nm, from about 1 nm to about 100 nm, fromabout 1 nm to about 400 nm, from about 1 nm to about 500 nm, from about2 nm to about 120 nm, from about 5 nm to about 150 nm, from about 5 nmto about 400 nm, from about 10 nm to about 300 nm, from about 20 nm toabout 400 nm, or from about 50 nm to about 250 nm.

In addition to the silanizing agents recited above, which can be used tomodify any one or more components of coatings (e.g., first and/or secondparticles), other agents can be employed including, but not limited to,one or more of: gamma-aminopropyltriethoxysilane, Dynasylan® A(tetraethylorthosilicate), hexamethyldisilazane, and Dynasylan® F 8263(fluoroalkylsilane), any one or more of which may be used alone or incombination with the silanizing agent recited herein.

5.2 Use of Compounds other than Silanizing Agents

Other agents also can be used to introduce hydrophobic and/or oleophobicmoieties into second particles. The choice of such agents will depend onthe functionalities available for forming chemical (covalent) linkagesbetween hydrophobic/oleophobic moieties and the functional groupspresent on the second particles surface. For example, where secondparticle surfaces have, or can be modified to have, hydroxyl or aminogroups, then acid anhydrides and acid chlorides of alkyl, fluoroalkyl,and perfluoroalkyl compounds may be employed (e.g., the acid chlorides:Cl—C(O)(CH₂)_(4 to 18)CH₃; Cl—C(O)(CH₂)₄₋₁₀(CF₂)_(2 to 14)CF₃;Cl—C(O)(CF₂)₄₋₁₈CF₃ or the anhydrides of those acids).

6.0 Solvents

6.1 Low VOC and VOC-Exempt Organic Solvents

Volatile organic compounds (VOC) means any compound of carbon, excludingcarbon monoxide, carbon dioxide, carbonic acid, metallic carbides orcarbonates, and ammonium carbonate, which participates in atmosphericphotochemical reactions. This includes any such organic compound otherthan the following, “exempt organic solvents” or “VOC-exempt solvents,”which have been determined to have negligible photochemical reactivity:methane; ethane; methylene chloride (dichloromethane);1,1,1-trichloroethane (methyl chloroform);1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113); trichlorofluoromethane(CFC-11); dichlorodifluoromethane (CFC-12); chlorodifluoromethane(HCFC-22); trifluoromethane (HFC-23); 1,2-dichloro1,1,2,2-tetrafluoroethane (CFC-114); chloropentafluoroethane (CFC-115);1,1,1-trifluoro 2,2-dichloroethane (HCFC-123); 1,1,1,2-tetrafluoroethane(HFC-134a); 1,1-dichloro 1-fluoroethane (HCFC-141b); 1-chloro1,1-difluoroethane (HCFC-142b); 2-chloro-1,1,1,2-tetrafluoroethane(HCFC-124); pentafluoroethane (HFC-125); 1,1,2,2-tetrafluoroethane(HFC-134); 1,1,1-trifluoroethane (HFC-143a); 1,1-difluoroethane(HFC-152a); parachlorobenzotrifluoride (PCBTF); cyclic, branched, orlinear completely methylated siloxanes; acetone; perchloroethylene(tetrachloroethylene); 3,3-dichloro-1,1,1,2,2-pentafluoropropane(HCFC-225ca); 1,3-dichloro-1,1,2,2,3-pentafluoropropane (HCFC-225cb);1,1,1,2,3,4,4,5,5,5-decafluoropentane (HFC 43-10mee); difluoromethane(HFC-32); ethylfluoride (HFC-161); 1,1,1,3,3,3-hexafluoropropane(HFC-236fa); 1,1,2,2,3-pentafluoropropane (HFC-245ca);1,1,2,3,3-pentafluoropropane (HFC-245ea); 1,1,1,2,3-pentafluoropropane(HFC-245eb); 1,1,1,3,3-pentafluoropropane (HFC-245fa);1,1,1,2,3,3-hexafluoropropane (HFC-236ea); 1,1,1,3,3-pentafluorobutane(HFC-365mfc); chlorofluoromethane (HCFC-31); 1 chloro-1-fluoroethane(HCFC-151a); 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a);1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxy-butane (C4F9OCH3or HFE-7100);2-(difluoromethoxymethyl)-1,1,1,2,3,3,3-heptafluoropropane((CF3)2CFCF2OCH3); 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane(C4F9OC2H5 or HFE-7200);2-(ethoxydifluoromethyl)-1,1,1,2,3,3,3-heptafluoropropane((CF3)2CFCF2OC2H5); methyl acetate,1,1,1,2,2,3,3-heptafluoro-3-methoxy-propane (n-C3F7OCH3, HFE-7000),3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-(trifluoromethyl) hexane(HFE-7500), 1,1,1,2,3,3,3-heptafluoropropane (HFC 227ea), methyl formate(HCOOCH3), (1)1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-trifluoromethyl-pentane(HFE-7300); propylene carbonate; dimethyl carbonate; and perfluorocarboncompounds which fall into these classes:

-   -   (i) Cyclic, branched, or linear, completely fluorinated alkanes;    -   (ii) Cyclic, branched, or linear, completely fluorinated ethers        with no unsaturations;    -   (iii) Cyclic, branched, or linear, completely fluorinated        tertiary amines with no unsaturations; and    -   (iv) Sulfur containing perfluorocarbons with no unsaturations        and with sulfur bonds only to carbon and fluorine.

6.2 The use of Solvents in Coating Compositions

Where compositions comprise significant amounts of solid components, itmay be desirable to dilute the compositions for ease of application,such as with VOC-exempt solvents including, but not limited to, waterand/or acetone or other water miscible VOC-exempt solvents in additionto water and any other liquids that are already present in thecomposition. In some embodiments it may be desirable to add non-VOCexempt solvents. Thus, in some embodiments solvents such as ethanol,isopropanol or n-propanol, alone or in any combination, may be added asdiluents. In one group of embodiments, the coating compositionsdescribed in this disclosure may be diluted with, and/or comprise:water; water and acetone; water and isopropanol and/or n-propanol; orwater, acetone, and isopropanol and/or n-propanol.

Typically water up to 50% or 60% may be used to dilute the coatingcomposition, but other amounts (e.g., 0.1-10, 10-20, 20-30, 30-40,40-50, or 50-60 percent by weight of the final composition) of water orone or more compatible solvents (e.g., acetone, isopropanol, n-propanoland/or ethanol), alone or in combination may be employed. If possible ordesired, the solvents added in addition to water will be VOC-exemptsolvents or contain less than 1, 2, 5, 10, 15, 20%, 25%, 30%, 35% or 40%of solvents that are not VOC exempt. Where application of the coatingsis to be conducted by rolling or brushing, the composition willtypically contain an addition amount of water from about 15% to about50% by weight of the composition (e.g., the compositions will be dilutedwith about 15 grams (g) to about 50 g of water per 100 g of the basecomposition). Similarly, where the compositions are to be applied byspraying, the composition can be diluted by addition of about 40 g toabout 60 g of water, or other solvents such as acetone, per 100 g of thecompositions as described herein. Mixtures of water and one or moreVOC-exempt solvents, such as water miscible VOC-exempt solvents, may beemployed for diluting composition to be applied by rolling, brushingand/or spraying.

In addition to reducing the thickness or viscosity of the compositions,solvents other than water provide a number potential benefits including,but not limited to, more rapid drying where the solvents are morevolatile than water. The addition of solvents other than water alsoincreases the ease in mixing components to form a uniformdispersion/suspension, and increases the stability of the suspension asmeasured by the length of time before the components once mixed willseparate. Compositions comprising one or more solvents other than water(e.g., acetone, isopropanol, or n-propanol) such as in the range of1-25% or 5-25% 10-25% or 10-20% (e.g., about 1%, 2%, 5%, 10%, 15%, 20%,or 25%) by weight of the final composition including the solvents, havea greater tendency to stay as suspensions, emulsions or dispersions fora longer period of time than compositions that are otherwise equivalentbut contain water in place of the solvent. In some embodiments thecompositions will continue to stay as suspensions, emulsions ordispersions for two, three, four, five, six, or ten times longer thancompositions that are otherwise equivalent but contain water in place ofthe solvent.

7. Application of Coatings

Coatings may be applied to substrates, or base coatings previouslyapplied to substrates, by any method known in the art, including but notlimited to: brushing, painting, dipping, spin coating, spraying, orelectrostatic spraying.

The composition may contain any necessary solvents/liquids, particularlywater or a VOC-exempt solvent, to assist in the application process, forexample by reducing the viscosity of the composition.

In some embodiments, the one-step SH and/or OP coatings described abovemay be treated to further modify their properties by the subsequentapplication of compositions comprising second particles and/orsilanizing agents. Such a composition, which may be termed a “topcoats,” is applied before the SH and/or OP coating has substantiallycured, typically 30-45 minutes after the application of the SH and/or OPcoating. When such top coatings are applied, other components of thecoating (e.g., the binder or first particles) may also become modifiedby the agent. Top coat compositions typically comprise a solvent (e.g.,a VOC-exempt solvent) and second particles from about 1 to about 20%weight/volume. Alternatively, the top coat may comprise a compound offormula I alone or in combination with silica particles having the sizeof a second particle. In one embodiment, the top coat comprises acetoneas a VOC-exempt solvent, and 1-5% fumed silica (w/v), about 0.25 toabout 2% tetrachlorosilane (SiCl₄ v/v), and from about 0.25 to about1.0% (v/v) of a silanizing agent, such as a compound of formula I.

Second particles, applied as part of a top coat composition in atwo-step method may be applied either as a suspension in a suitablesolvent that is compatible with the binder system (e.g., a low VOCcomposition, hexane, xylene, and ethanol) or without a solvent using aspray gun (air spray gun) supplied with a suitable supply of compressedair, nitrogen, or other compressed gas (e.g., a Binks Model 2001 or2001V spray gun air spray gun; Binks, Inc., Glendale Heights, Ill,supplied with air at about 50 psi may be employed). Thus, in someembodiment the top coating composition is applied by spraying oratomizing a liquid second composition onto the SH and/or OP coating.Alternatively, the second particles are applied absent any liquid byspraying the SH and/or OP coating with second particles using a streamof gas.

8. Surface Preparation

To provide good adhesion of coatings to a surface, the surfaces may becleaned and may also be abraded to create some degree of surfaceroughness. Surface roughness can be created by methods including: (1)scuffing with an abrasive pad (e.g., Scotch-Brite™ pads), (2) finesandblasting, (3) tumble blasting with small steel balls, and (4) coarsesandblasting.

The surface roughness of coatings, or the roughness of substratesproduced by different methods, can be measured using a Mahr Pocket SurfPS1 (Mahr Federal Inc., Providence, R.I.) and can be expressed using avariety of mathematical expressions including, but not limited to, thearithmetical mean roughness (Ra) and ten-point mean roughness (Rz),which are described in FIG. 33.

Scuffing surfaces, such as plastic, with abrasive materials such asScotch-Brite™ pads increases the roughness values of plastics to an Raof about 0.2-0.3 μm to about 0.7-0.9 μm and the Rz from about 1.4 toabout 7 μm. Sandblasting plastics with coarse sand produces a very roughsurface where the Ra increases substantially into the range of about 5to about 6 μm and the Rz increases to the range of about 30 to about 37μm.

The surface of flexible materials, can also be abraded to improve theadherence of the SH and/or OP coatings. Scuffing with abrasive materials(e.g., Scotch-Brite™ pads) can increase the Ra of flexible materialssuch as rubber from the range of about 0.2 to about 0.35 μm to the rangeof about 0.4 to about 0.5 μm and the Rz from about 2 μm to the range ofabout 3 to about 4 μm. Fine sandblasting of flexible materials, such asrubber, increases the Ra into the range from about 0.60 to about 0.75 μmand the Rz from about 2 μm to the range from about 6 to about 7 μm.Tumbling plastics with small steel balls can increase the Ra from about0.28 to the range of about 0.3 to about 0.4 μm and the Rz from about2.043 to about 3.28 μm. Coarse sandblasting increases the Ra from 0.3 tothe range of about 5 to about 6 μm and the Rz to the range of about 30to about 35 μm.

9. Use of Hydrophobic and/or Oleophobic Coating

The compositions described herein may be used to apply superhydrophobicand/or oleophobic coatings to on many, if not most surfaces including,but not limited to metals, glasses, ceramics, stone, rubbers, fabrics,and plastics to achieve a variety of desirable results. The coatings maybe employed for a variety of uses including preventing or resisting theattachment of water, dirt and/or ice to the surfaces. Due to theirproperties, the surfaces may be employed in applications including, butnot limited to, anti-corrosion, anti-icing, self-cleaning, andliquid/spill containment.

In one embodiment, may be applied to electrical equipment to prevent icefrom forming and causing damage through corrosion or arching. In oneparticular embodiment, the electrical equipment is high voltageinsulators and/or wires exposed to rain, snow or ice. In anotherembodiment the electrical equipment are transformers, electrical powerboxes, electric motor windings, and/or electrical switches.

In another embodiment, the coatings are applied to aircraft (e.g., wingsand/or control surfaces) to prevent ice formation.

In another embodiment, the coatings are applied to surfaces of marineequipment exposed to temperatures that will freeze fresh and/or seawater (e.g., rails, ladders, booms, hatches, dock components, and thelike) to prevent ice formation.

Coating compositions described herein can be employed in otherembodiments, to form spill resistant borders on shelves, counters, workareas or floors.

Another use of the coating compositions described herein is thepreparation of self-cleaning sidings, window frames, gutters, satellitedishes, lawn furniture, and other outdoor products.

The coatings described herein can be used for corrosion protection inthe automotive industry. In one embodiment, the coatings can be used forcorrosion protection on underside of cars, trucks, and other heavy-dutyequipment/vehicles.

10. Coating Compositions

Some exemplary ranges for the SH and/or OP coating components aredescribed in the table below. Each component (Binder, First Particles,Second Particles, and Third Particles) may be combined with the othercomponents in any of the ranges set forth in the table below, providedthe components do not total to more than 100%.

Component Polyurethane Second Third Binder First Particles ParticlesParticles Ranges Min-Max % Min-Max % Min-Max % Min-Max % 1 30-50 2 35-474 30-35 5 35-40 6 40-45 7 45-50 8 50-60 1  1-35 2  0-7  3  0-4  4  4-8 5 10-15 6 15-20 7 20-25 8 25-30 9 30-35 1 7.5-25 2   8-22 3   9-20 4 10-21 5   8-16 6   9-18 7 7.5-10 8  10-15 9  15-20 10  20-25 1  0 2  0-26 3  0>-3  4 0.1-3  5   3-6  6   3-9  7   6-9  8   6-12 9  12-15 10 15-20 11  20-26

Percentages as recited in the preceding table and in the specificationare based on the total weight of the compositions. Unless statedotherwise, the composition percentages given for the polyurethanebinders represent the weight of the polyurethane binder as provided bytheir commercial suppliers, which contain from about 34% to 46%polyurethane binder components on a dry weight basis. Dry weightcomposition ranges for the binder components may determined based uponthose ranges. Where, component do not total to 100%, the balance istypical comprised of water and/or other solvents (e.g., VOC-exemptsolvents such as acetone or acetone water combinations). In otherembodiments, it may be desirable to add non-VOC exempt solvents. In someembodiments solvents that are not VOC-exempt, such a isopropanol orn-propanol, may be added. Thus, in one group of embodiments, the coatingcompositions described in this disclosure may be diluted with, and/orcomprise a solvent that is containing: water; water and acetone; waterand isopropanol and/or n-propanol; or water, acetone, and isopropanoland/or n-propanol.

Thirty four SH/OP coating compositions comprising the above-mentionedcomponents are set forth in the following table. As with the tableabove, all recited percentages are based on the total weight of thecomposition, with the balance typically being comprised of one or morecompatible VOC-exempt solvents such as water. Once prepared, thecompositions may be diluted with one or more compatible solvents (e.g.,water) to control properties (e.g., viscosity) for application.Typically up to 50% water may be used to dilute the coating composition,but other amounts (e.g., 0.1-10, 10-20, 20-30, 30-40, 40-50, or 50-60percent by weight of the final composition) of one or more compatiblesolvents (e.g., acetone, isopropanol, n-propanol and/or ethanol), aloneor in combination may be employed. If possible or desired, the solventsadded in addition to water will be VOC-exempt or contain less than 1, 2,5, 10, 15, or 20% of solvents that are not VOC exempt. Where applicationof the coatings is to be conducted by rolling or brushing, thecomposition will typically contain an addition amount of water fromabout 15% to about 50% by weight of the composition (e.g., thecompositions will be diluted with about 15 g to about 50 grams of waterper 100 g of the base composition). Similarly, where the compositionsare to be applied by spraying, the composition can be diluted byaddition of about 40 g to about 60 g of water or other solvents orcombinations of solvents (such as acetone) per 100 g of the compositionas described herein. Mixtures of water and one or more VOC-exemptsolvents may be employed for diluting composition to be applied byrolling, brushing and/or spraying.

Component Polyurethane First Second Third Binder Particles ParticlesParticles Polymer Min-Max Min-Max Min-Max Composition Min-Max % % % % 132-47 0  5-15 0 2 32-47 0 10-21 0 3 32-47 1-7  5-15 0 4 32-47 1-7 10-210 5 32-47 1-7  5-15 0 6 32-47 1-7 10-21 0 7 32-47 0  5-15 0 8 32-41 010-21 0>-10 9 32-41 1-7  5-15 0>-10 10 32-41 1-7 10-21 0>-10 11 32-411-7  5-15 0>-10 12 32-41 1-7 10-21 0>-10 13 32-41 0  5-15 10-26 14 32-410 10-21 10-26 15 32-41 1-7  5-15 10-26 16 32-41 1-7 10-21 10-26 17 32-411-7  5-15 10-26 18 32-41 1-7 10-21 10-26 19 30-39 0  5-15 0 20 30-39 010-21 0 21 30-39 1-7  5-15 0 22 30-39 1-7 10-21 0 23 30-39 1-7  5-15 024 30-39 1-7 10-21 0 25 30-39 0  5-15 0 26 30-39 0 10-21 0>-10 27 30-391-7  5-15 0>-10 28 30-39 1-7 10-21 0>-10 29 30-39 1-7  5-15 0>-10 3030-39 1-7 10-21 0>-10 31 30-39 0  5-15 10-26 32 30-39 0 10-21 10-26 3330-39 1-7  5-15 10-26 34 30-39 1-7 10-21 10-26A skilled artisan will understand that composition anges of individualcomponents may b selected so that they do not exceed 100%.

In addition to their hydrophobicity and oleophobicity (e.g.,superhydrophobicity and/or superoleophobic) the coatings described inthe present disclosure have a variety of other properties such asflexibility without loosing their hydrophobicity or oleophobicity. Insome embodiments, the coatings compositions when applied to flexiblerubber sheet approximately one eighth of an inch thick, then dried andcured, can be brought to a ninety degree angle around a cylindrical rodgreater than 2, 4, 8, 10, 20, 40, 50, 75, 100, or 200 times at roomtemperature (18 to about 23° C.) without loss of the coating'shydrophobic or oleophobic properties (e.g., remaining hydrophobic oroleophobic or even superhydrophobic and/or superoleophobic).

A skilled artisan will understand that composition ranges of individualcomponents may be selected so that they do not exceed 100%. Wherecompositions comprise significant amounts of solid components, it may bedesirable to dilute the compositions for ease of application, such aswith VOC-exempt solvents in addition to any other liquids that arealready present in the composition.

Certain embodiments are described below.

1. A coating composition for the application/preparation of hydrophobic(e.g., superhydrophobic) and/or oleophobic (e.g., superoleophobic)coatings on surfaces comprising:

-   -   a polyurethane dispersion or suspension comprising one or more        of a polyester urethane, a polyacrylic urethane and/or a        polycarbonate urethane;    -   about 5 to about 30% by weight of second particles comprising        one or more siloxanes, and/or one or more alkyl, haloalkyl,        fluoroalkyl, or perfluoroalkyl containing moieties;    -   said composition optionally comprising up to about 26% by weight        of third particles;

wherein said coating composition optionally comprises less than about0.6, 0.5, 0.4, or 0.3 pounds per gallon of volatile non-exempt organiccompounds; and

wherein the superhydrophobic coating resulting from the application ofsaid composition to a surface retains its superhydrophobicity after150-1,400 Taber abrasion cycles at a 1000 g load for coating thicknessrange of 25-300 microns, and/or 100-2,500 Taber abrasion cycles at a 250g load, using a CS10 wheel, as judged by the inability of more than 50%of the water droplets applied to the area of the coating subjected tosaid abrasion cycles to remain on the surface when the planar surface isinclined at 3 degrees.

2. The composition of any of embodiment 1, wherein said polyurethanesuspension or dispersion does not comprise third particles.

3. The composition of embodiment 2, wherein said composition does notcomprise first particles and the superhydrophobic coating resulting fromthe application of said composition to a planar surface retains itssuperhydrophobicity after 150-800 Taber abrasion cycles at a 1,000 gload, for a thickness range of 25-75 microns, and/or 200-1,400 Taberabrasion cycles at a 250 g load for a thickness range of 25-75 microns,on a planar surface using a CS10 wheel, as judged by the inability ofmore than 50% of the water droplets applied to the area of the coatingsubjected to said abrasion cycles to remain on the surface when theplanar surface is inclined at an angle of 3 degrees.

4. The composition of embodiment 1, wherein said composition furthercomprises first particles.

5. The composition of embodiment 4, wherein the composition comprises5-20% by weight of first particles.

6. The composition of embodiment 5, wherein the first articles, areselected from oxides of metalloids, metal oxides, one or morethermoplastics, one or more thermoset plastics, one or more metals, oneor more glasses, and/or one or more hollow spheres.

7. The composition of any of embodiments 4 to 6, wherein thesuperhydrophobic coating resulting from the application of saidcomposition to a planar surface retains its superhydrophobicity after100-600 Taber abrasion cycles at a 250 g load for a thickness range of40-85 micron using a CS10 wheel, as judged by the inability of more than50% of the water droplets applied to the area of the coating subjectedto said abrasion cycles to remain on the surface when the planar surfaceis inclined at an angle of 3 degrees.

8. The composition of any of embodiment 1, wherein said polyurethanesuspension or dispersion comprises third particles.

9. The composition of embodiment 8, the composition comprises 5-20% byweight of third particles.

10. The composition of any of embodiments 8 to 9, wherein the thirdparticles, are selected from particles comprising one or more inorganiccompounds, one or more oxides of metalloids or metal oxides.

11. The composition of any of embodiments 8 to 10, wherein saidcomposition does not comprise first particles and the superhydrophobiccoating resulting from the application of said composition to a planarsurface retains its superhydrophobicity after about 300-350 Taberabrasion cycles at a 1000 g load, for a thickness range of 25-75 micronsand/or 400-800 Taber abrasion cycles at a 250 g load, for a thicknessrange of 25-80 microns on a planar surface using a CS10 wheel, as judgedby the inability of more than 50% of the water droplets applied to thearea of the coating subjected to said abrasion cycles to remain on thesurface when the planar surface is inclined at an angle of 3 degrees.

12. The composition of any of embodiments 8-10, further comprising firstparticles.

13. The composition of embodiment 12, wherein the composition comprises5-20% by we of first particles.

14. The composition of any of embodiments 12 to 13, wherein the firstparticles, are selected from oxides of metalloids, metal oxides, one ormore thermoplastics, one or more thermoset plastics, one or more metals,one or more glasses, and/or one or more hollow spheres.

15. The composition of any of embodiments 12 to 14, wherein thesuperhydrophobic coating resulting from the application of saidcomposition to a planar surface retains its superhydrophobicity after200-1,400 Taber abrasion cycles at a 1000 g load, for a thickness rangeof 75-300 microns and/or 400-2,500 Taber abrasion cycles at a 250 gload, for a thickness range of 35-90 microns on a planar surface using aCS1.0 wheel, as judged by the inability of more than 50% of the waterdroplets applied to the area of the coating subjected to said abrasioncycles to remain on the surface when the planar surface is inclined atan angle of 3 degrees.

16. The composition of any of embodiments 1 to 16, w herein said one ormore of a polyester urethane, a polyacrylic urethane and/or apolycarbonate ethane are a BAYHYDROL® and/or a POLANE®.

17. The composition of any of embodiments 1 to 15, wherein thecomposition comprises a mixture of polyacrylic urethanes andpolycarbonate urethanes.

18. The composition of embodiment 17, wherein said aqueous polyurethanedispersion or suspension comprises a mixture of at least two of: apolyester urethane, an aliphatic polyester urethane, a polycarbonateurethane a polyacrylic urethane, and an aliphatic polycarbonate urethane

19. The composition of embodiment 18, wherein said mixture comprises aBAYHYDROL® and a POLANE®.

20. The composition of embodiment 19, wherein said are comprises a ratioof BAYHYDROL® to POLANE® from 90:10 to 50:50.

21. The composition of embodiments 18 to 20, wherein said BAYHYDROL® isBAYHYDROL® 124, 122, 110 or 140AQ.

22. The composition of any of embodiments 18-22 wherein said POLANE® isPOLANE® 700T,

23. The composition of any of embodiments 1 to 22, wherein saidcomposition further comprises second particle have a size of about 2 nmto about 120 nm.

24. The composition of any of embodiments 1 to 22, wherein said secondparticle have a size of about 1 nm to up to about 25 microns

25. The composition of embodiment 24, wherein said particles are silicaparticles.

26. The composition of any of embodiments 1 to 24, wherein said siloxaneis polydimethylsiloxane.

27. The composition of any of embodiments 1 to 25, wherein said one ormore alkyl, haloalkyl, fluoroalkyl, or perfluoroalkyl containingmoieties are one or more alkylsilane, haloalkylsilane, fluoroalkylsilaneor perfluoroalkylsilane groups.

28. The composition of embodiment 27, wherein said alkyl, haloalkyl,fluoroalkyl, fluoroalkylsilane and/or perfluoroalkylsilane groups resultfrom the reaction of silica or metal oxide particles with one or moresilanes selected from the group consisting of: a compound of formula I,(tridecafluoro-1,1,2,2-tetrahydrooctyl)silane (SIT8173.0);(tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane (SIT8174.0);(tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane (SIT8175.0);(tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane (SIT8176.0);(heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethyl(dimethylamino)silane(SIH5840.5);(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tris(dimethylamino)silane(SIH5841.7); n-octadecyltrimethoxysilane (SIO6645.0);n-octyltriethoxysilane (SIO6715.0); and3,3,4,4,5,5,6,6,6-nonafluorohexyldimethyl(dimethylamino)silane(SIN6597.4).

29. The composition of embodiment 27, wherein said alkylsilane and/orfluoroalkylsilane result from the reaction of silica or metal oxideparticles with one or more silanes selected from the group consistingof: tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane;(tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane;nonafluorohexyldimethylchlorosilane;(tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane;3,3,4,4,5,5,6,6,6-nonafluorohexyldimethyl(dimethylamino)-silane;nonafluorohexyhnethyldichlorosilane; nonafluorohexyltrichlorosilane;nonafluorohexyltriethoxysilane; and nonafluorohexyltrimethoxysilane.

30. The composition of any of the preceding embodiments wherein saidsecond particles are present from about 20 to about 30% by weight.

31. The composition of any of embodiments 1-30, wherein said secondparticles are present in an amount from about 5 to about 20% by weight.

32. The composition of embodiment 31, wherein said second particles arepresent in an amount from about 10 to about 12% by weight.

33. The composition of any of embodiments 1 to 32, wherein said coatingis both superhydrophobic and oleophobic.

34. The composition of any of embodiments 4 to 7, 14 to 33, comprisingtwo or more, or three or more, types of first particles having differentcompositions.

35. The composition of any of embodiments 4 to 7, 14 to 34, comprising athermoplastic or thermoset plastic first particle.

36. The composition of embodiment 35, wherein said thermoplastic orthermoset plastic first particle comprise about 5 to about 10% of thecomposition by weight.

37. The composition any of embodiments 4 to 7, 14 to 34, comprisingglass bead or hollow glass sphere first particles.

38. The composition of embodiment 37, wherein said glass bead or hollowglass sphere first particles comprise about 5 to about 15% of thecomposition by weight.

39. The composition of embodiment 38, wherein said glass bead or hollowglass sphere first particles comprise about 6 to about 8% of thecomposition by weight.

40. The composition of any of the preceding embodiments, that when driedand cured produces a surface with an arithmetic mean roughness (Ra) ofless than about 30 microns

41. The composition of any of the preceding embodiments, that when driedand cured produces a surface with an arithmetic mean roughness (Ra) ofless than about 20 microns

42. The composition of any of the preceding embodiments, that when driedand cured produces a surface with an arithmetic mean roughness (Ra) ofless than about 16 microns

43. The composition of embodiment 40, wherein said arithmetic meanroughness (Ra) is from about 1 to about 20 microns.

44. The composition of any of embodiments 1-43, comprising from about30% to about 50% polyurethanes by weight.

45. The composition of any of embodiments 1-44, wherein saidpolyurethane dispersion or suspension comprise at least one polyesterurethane, polyacrylic urethane, and/or polycarbonate urethanecomposition that when dried and cured produces a coating that has: (a) amodulus at 100% elongation of 1300 psi or greater, and/or (b) anelongation percent at break of 150% or greater.

46. The composition of any of embodiments 1-45, further comprising0.1-10, 10-20, 20-30, 30-40, 40-50 or 50-60 g of one or more compatiblesolvents per 100 g of coating composition.

47. The composition of embodiment 46, wherein said one or morecompatible solvents are VOC-exempt solvents such as a water, acetone ora combination of water and acetone, and wherein said coating compositioncomprises less than about 0.5, 0.4, 0.3, or 0.2 pounds per gallon ofvolatile non-exempt organic compounds.

48. The composition according to embodiment 47, w herein said one ofmore solvents that are not VOC-exempt solvents (non-VOC-exemptsolvents), or solvents compositions that comprise solvents that are notVOC-exempt solvents such as: ethanol; isopropanol or n-propanol; waterand isopropanol and/or n-propanol; acetone and isopropanol and/orn-propanol; or water, acetone, and isopropanol and/or n-propanol.

49. A hydrophobic (superhydrophobic) and/or oleophobic (superoleophobic)coating formed by the application of the composition of any embodiments1-48.

50. A method of coating at least part of a surface comprising theapplication of a composition of any of embodiments 1-48.

51. The method of embodiment 50, wherein said method comprises dipping,spraying, rolling, or spin coating said composition onto said surface.

52. The method of any of embodiments 50 or 51, further comprising dryingthe coating composition at an elevated temperature (e.g., at about 120,140, 160, 180, 200, 220, or 240 degrees Fahrenheit)

53. The method of any of embodiments 50-52, further comprising applyinga top-coat to said coating.

54. The method of embodiment 53, wherein said top-coat comprises secondparticles (e.g., fumed silica) treated to be hydrophobic (e.g.,particles treated with a silanizing agent such as those described insection 5.0 including, but not limited to, silanizing agents of formulaI) or wherein said top-coat comprises a silanizing agent (e.g., asilanizing agent such as those described in section 5.0 including, butnot limited to, silanizing agents of formula I).

55. A coating prepared by the method of any of embodiments 50-54.

56 The coating of embodiments 49 or 55, wherein in said coating furthercomprises a top-coat of second particles treated to be hydrophobic(e.g., treated with a silanizing agent such as those described insection 5.0 including, but not limited to, silanizing agents of formulaI) or the coating further comprising a top-coat of a hydrophobic silanegroup (e.g., a surface treated with silanizing agent such as thosedescribed in section 5.0 including, but not limited to, silanizingagents of formula I).

57. The coating of any of embodiments 49 and 55-56, that when dried andcured produces a surface with an arithmetic mean roughness (Ra) in arange selected from: about 0.2 μm to about 20 μm; about 0.3 μm to about18 μm; about 0.2 μm to about 8 μm; about 8 μm to about 20 μm; or about0.5 μm to about 15 μm; or a roughness that is less than about 30microns, 20 microns, 16 microns or 10 microns.

58. The coating of any of embodiments 49 and 55-57, wherein saidpolyurethane dispersion or suspension comprise at least one polyesterurethane, polyacrylic urethane, and/or polycarbonate urethanecomposition that when dried and cured produces a coating that has: (a) amodulus at 100% elongation of 1300 psi or greater, and/or (b) anelongation percent at break of 150% or greater.

59. The coating of any of embodiments 49 and 55-58, that retains itshydrophobicity (superhydrophobicity) and/or its oleophobicity(superoleophobicity) after a flexible substrate (about ⅛ inch inthickness) coated with said coating is bent greater than 100 times aright angle around a cylinder with a diameter of ¼ inch.

60. The coating composition of any of embodiments 49 and 55-59, whereinsaid second particles are dispersed throughout the coating thickness,and wherein said coating retains its hydrophobicity(superhydrophobicity) and/or its oleophobicity (superoleophobicity)after abrasion.

61. The coating of any of embodiments 49 and 55-60, that retains itshydrophobicity (superhydrophobicity) and/or its oleophobicity(superoleophobicity) after being exposed to rain or a shower for morethan 1 hour.

EXAMPLES

For the purposes of this disclosure a hydrophobic coating is one thatresults in a water droplet forming a surface contact angle exceedingabout 90° and less than about 180° at room temperature (about 18 toabout 23° C.). Similarly, for the purposes of this disclosure asuperhydrophobic (SH) coating is one that results in a water dropletforming a surface contact angle exceeding about 150° but less than thetheoretical maximum contact angle of about 180° at room temperature. Theterm hydrophobic includes superhydrophobic, and may be limited tosuperhydrophobic, unless stated otherwise.

Superhydrophobicity may be assessed by measurement of the contact angleof water droplets with the surface. Where contact angles are notprovided or determined directly, the superhydrophobicity of a coating,and particularly the loss of superhydrophobicity after abrasion testing,may be determined by placing water droplets on a coated surface inclinedat 3°. Where more than half of the water droplets remain on the surfacewhen it is inclined to 3°, the coating is deemed to have lost itssuperhydrophobicity.

For the purposes of this disclosure an oleophobic (OP) coating is onethat results in a light mineral oil droplet forming a surface contactangle exceeding about 90° and less than about 180° at room temperature(about 18 to about 23° C.). Similarly, for the purposes of thisdisclosure a superoleophobic coating is one that results in a waterdroplet forming a surface contact angle exceeding about 150° but lessthan the theoretical maximum contact angle of about 180° at roomtemperature. The term oleophobic includes superoleophobic, and may belimited to superoleophobic, unless stated otherwise.

Example 1: Effect of BAYHYDROL® Type Binder in One-Step Coating and itsPerformance in Two Systems

Binder Compositions

Coating compositions comprising two water-based (waterborne)polyurethanes as binders; a clear BAYHYDROL® (e.g., BAYHYDROL® 110, 122,124, A145, or 140AQ) and a POLANE® (e.g., POLANE® 700T) were prepared.For each composition in System 1 a BAYHYDROL® and a POLANE® werecombined in various ratios having from 40% to 70% BAYHYDROL® and from60% to 30% POLANE® 700T on a weight to weight basis (w/w), based on thecomposition as provided by the commercial suppliers (e.g., 4:6 to 7:3ratios of those components). The binder compositions contained thirdparticles (pigment) where it is indicated that they were “white”, andmay also contain third particle functioning as extenders. The combinedsystem can be further diluted with up to 50% water (by weight). Thecombined BAYHYDROL®-POLANE® binder system was used in two differentmodes discussed below.

Example 1A—One-Step Compositions

Fumed silica, or other second particles, pretreated with siloxane, wereadded to the above—described binder composition. Second particles wereadded in amounts ranging from about 5% to about 20% of the compositionby weight. Particle size, surface area, and treatments of various fumedsilica particles used are given in Table 1.

The composition of this mode may have water additions of up to 50% byweight based upon the weight of the binder composition as describedabove. Once all components were added to the binder (e.g., secondadded), the complete compositions were mixed well using steel balls or alow shear mixer. The mixed composition was applied to various substratesusing an air spray gun or other means as indicated (e.g., roller)effective to apply a coating to at least a portion of a surface. Once acoating was applied, the surfaces were cured at ambient conditions(65-85° F.) in 12-16 h. The cured coatings were superhydrophobic withwater contact angles over 150°. The compositions containing allcomponents were essentially VOC-free as no solvents that were notVOC-exempt were used (see Details in the Description). In a variation ofthe above-described one-step method, a top coating, as described hereinbelow Example 1B, can be applied over the one-step coating to enhance oralter its properties.

Example 1B—One-Step Compositions with Top Coat Treatment

To the compositions of Example 1A one or more of the first particles(filler particles) from the list in Table 2 are added. First particlescan comprise from up to 20% (e.g., 5-20%) of the composition by weight.

In some embodiments, a top coat can be applied to the SH or OP coatingdescribed herein, such as the compositions of Example 1A or 1B, tofurther modify the properties of the coatings. In one embodiment, thetop coat comprises acetone, as a VOC-exempt solvent and 1-5% fumedsilica (w/v), optionally about 0.25 to about 2% tetrachlorosilane (SiCl₄v/v), and from about 0.25 to about 1.0% (v/v) of a silane such as acompound of formula I or one of the specific silanizing agents recitedin Section 5.1. In addition to the foregoing components, about 0.1 toabout 1% v/v water can be added. In another embodiment, the top coat maycomprises acetone, as a VOC-exempt solvent and 1-5% of second particles(e.g., w/v in g/ml) and may optionally contain about 0.25 to about 2%tetrachlorosilane (SiCl₄ v/v), and from about 0.25 to about 1.0% (v/v)of a silane such as a compound of formula I or one of the specificsilanizing agents recited in Section 5.1.

When a top coat is applied it is typically applied by with air spray gunto base coats are close to completely (100%) dry. The typical dryingtime for SH and/or OP coats can vary from 45-90 min, at which time theyare ready for top coating. In another embodiment, surfaces may be coateda composition described in Example 1A and 1B that has been modified toomit second particles, and then given a top coat. In such a case thecoating composition serves as a base coat (similar to a primer) to whicha top coat can be applied to obtain the SH and OP performance.

Examples for Systems 1 and 2

Coating compositions comprising a BAYHYDROL® (124, 122, 110, A145, or140AQ, Bayer Material Science) were mixed with POLANE® 700T (productF63W522, white and applied to metal plates. The durability of the SHand/or OP coatings (resistance of the loss of SH and/or OP properties toabrasion) formed from the compositions were measured. In each case, theBAYHYDROL® and 700T, as prepared by the manufacturer, were mixed in aratio of 60:40 by volume. To each 100-g mixture was added 7 g of Corvelblack as a first particle, 11-g TS720 fumed silica, and 50-g water. Themixtures were agitated using low shear mixer to distribute the TS720uniformly in the composition. In each case, the solution was sprayed onaluminum plates to approximately the same thickness. After spraying, theplates were air-dried for 30 min followed by curing for 30 min in anoven at 200° F. On testing, the cured plates all displayedsuperhydrophobicity and were tested for loss of that property using aTaber tester with a 250-g load (CS10 wheel) by assessing the ability ofwater droplets applied to the abraded surface to roll off when it wasinclined at 3 degrees. The failure of more than half of the droplets toroll off the surface was taken as an indiction of a loss ofsuperhydrophobicity. The Taber data from the coatings formed from thevarious BAYHYDROL® containing compositions are summarized in Table 3.That table also includes the key physical, chemical, and mechanicalproperties of various BAYHYDROL®s. Taber data for various BAYHYDROL®containing compositions is also compared in FIG. 1.

Compositions comprising POLANE 700T and BAYHYDROL® 140AQ gave the mostabrasion resistant SH and/or OP coatings with a 250 g load (two coatingswere also assessed with a 1,000 g load). BAYHYDROL® 140AQ while similarto other BAYHYDROLs listed in Table 3 has several distinguishingcharacteristics including its cosolvent (Toluene which is present insmall amounts, 1%), its high tensile elongation, low modulus of 800 psi,and low hardness (F vs. H and 2H for others). BAYHYDROL® 140AQ ispolyester-based, and comprises sodium sulfinate functionality. While notwishing to be bound by any theory, it is believed that the sodiumsulfinate can serve as a surfactant and aid in distributing fumed silicaparticles (TS720) more uniformly throughout the entire coatingthickness. Based on that hypothesis, one-step coating based onBAYHYDROL®s 124, 122, 110, and A145, which have second particleslocalized near the surface are shown diagrammatically in FIG. 2(a). Incontrast, one-step coatings formed with BAYHYDROL® 140AQ, which arebelieved to have the second particles distributed throughout thecoating, are diagramed in FIG. 2(b). The schematic in FIG. 2 shows oneinterpretation for the loss of some or all of the superhydrophobicity incoatings such as those depicted in FIG. 2(a). Those coatings would loosesuperhydrophobicity once the top of the coating bearing second particlesis worn away. The schematic in FIG. 2(b) shows one interpretation forthe continued superhydrophobicity of coatings with second particlesdispersed throughout the coating thickness even as the coating isabraded, until it reaches bare metal. Coatings shown in FIG. 2(b) showthickness dependence wear and their ability to withstand increasingnumbers of Taber abrasion cycles increases with increasing coatingthickness as is shown, for example, in Example 2.

TABLE 3 Properties of Various BAYHYDROL ®s used in Developing One-StepSuperhydrophobic Coatings Mod- Tabers No. Water ulus 1000 of Co- Elon-at Cycles Ta- Co- Co- sol- gation 100% @ Bay- ber Vis- Sol- sol- sol-vent Tensile at Elon- 1000 g Swell after 24 h (%) Ureth- hydrol Cy-cosity ids vent vent (wt Strength Break gation (mg Hard- Wa- Xy- aneType cles ph (mPa/s) (%) Type (%) %) (psi) (%) (psi) loss) ness ter IPAMEK lene Type 124 50 7.0-  50- 35 + NM2P 12 53 5000 275 1300 H 5 15 5050 Poly 9.0  400 _2 cabon- ate 122 75 7.0-  50- 35 + NM2P 15 50 5000 1504100 28 2H 5 20 45 30 Poly 9.0  400 _2 cabon- ate 110 100 7.5-  50- 35 +NM2P 15 50 5900 180 4200 12 2H 10 25 35 20 Poly- 9.5  400 _2 ester A145125 7.5-  400- 43- Naph- 4 45.6 Poly- 8.5 1500 47 tha acry- 100 lic 2- 4butoxy- ethanol 140AQ 375 6.0-  100- 40 + Tol- 1 59 5300 450 800 F 10 20105 50 Poly- 8.0  700 _2 uene ester Abbreviations and notations:NM2P-N-methyl-2-pyrolidone Hardness on Pencil Lead scale as reported bymanufacturer (pencil lead hardness) F-Firm; H hard, 2H

Example 2: Coating Thickness Effect Using BAYHYDROL® 140AQ

A 60:40 mixture of BAYHYDROL® 140AQ and Plane 700T was made on a volumebasis using compositions as distributed by the manufacturer. To 100 g ofthe mixture was added 7-g Tiger Drylac clear matte powder (Series 49),11-g of CAB-O-SIL® TS720, and 50-g water. The mixture was prepared bylow shear mixing and applied by spraying with an air gun with 40 psipressure) on to steel (4 by 4 inch (in.) plates of 0.062-in. thickness).Steel plates were used for ease of measuring the coating thickness usinga magnetic-based sensor (Model 95520 Digital Gauge, Cen-Tech, Taiwan). Atotal of seven plates were sprayed and tested for coating thickness,surface roughness, and resistance to wear (i.e., Taber cycles 250-gload). Data on the plates are summarized in Table 4, which shows thecoating thickness varied from 10-68 μm (0.4-2.7 mils) and the surfaceroughness increased with increasing thickness (FIG. 3) from R_(a)=2.59μm to R_(a)=12.56 μm. The Taber cycles increased approximately linearlywith thickness (see FIG. 4) from 40 to 800, an increase of 20× from thethinnest to the thickest coating. The line in FIG. 4 can be used as aguide to selecting the coating thickness for a defined Taber durability.The Taber durability also appears to increase with increasing surfaceroughness as indicated in FIG. 5.

TABLE 4 Taber and Surface Roughness Data on Steel Plates Coated withOne-Step System using BAYHYDROL ® 140AQ Coating Surface CoatingThickness Tabers Roughness, R_(a) Thickness (mils) (Cycles) (μm) (μm)0.4 40 2.59 10.16 0.7 100 4.69 17.78 0.9 195 4.55 22.86 1.1 240 8.8927.94 1.9 600 12.40 48.26 2.2 750 12.32 55.88 2.7 800 12.56 68.58

Example 3: Variation on Second Particle Content in a One-Step CoatingsPrepared with BAYHYDROL® 140AQ/Clear 700T Binder and CAB-O-SIL® TS720Ranging from 11-20%

A 60:40 mixture of BAYHYDROL® 140AQ and clear POLANE® 700T (F63V521) byvolume was prepared using those products as distributed by theirmanufacturers. To 40 g amounts of each mixture was added 4.4, 6.0, and8.0 g (i.e., 11%, 15%, and 20%) of CAB-O-SIL® TS720. Also added to eachmixture was 20-g (50%) water. All percentages are calculated and basedon 100 g of 60:40 mixture. The compositions were each mixed using steelhalls or a low impact mixer.

Each mixture was sprayed (using an air gun) on 4×4-in square steelplates at five different thicknesses. All of the plates were air-driedfor 30 min prior to drying in an oven at 200° F. for 30-40 min. Eachplate was subjected to thickness measurement, surface roughnessmeasurement (R_(a) and R_(z) values), and wear resistance using a Taberabrader (Taber abrasion). All Taber abrasion measurements were obtainedusing 250-g load and CS10 wheels. Data are summarized in Table 5 andplotted in FIGS. 6-8. FIG. 6 and shows the plot of surface roughness,R_(a) and R_(z) values respectively. FIG. 8 shows Taber data as afunction of coating thickness.

TABLE 5 Summary of Data for One-Step Coating on Steel Plates made withBAYHYDROL ® 140AQ and clear 700T: Fumed Silica TS720 Varied from 11-20%Number of Coating Thickness Tabers R_(a) R_(z) Thickness Coating Plate #(mils) 250-g Load (μm) (μm) (μm) 40.0 g Bay 1.1 0.93 300 3.36 23 23.62140/700T Clear 1.2 1.47 650 7.02 36.8 37.34 (60/40), 4.4 g 1.3 1.46 3005.52 33.7 37.08 TS720, 20.0 g 1.4 2.29 1500 8.21 41.4 58.17 Water 1.52.2 750 10.35 55.3 55.88 40.0 g Bay 2.1 1.01 150 5.79 31.7 25.65140/700T Clear 2.2 1.34 450 7.44 43.2 34.04 (60/40), 6.0 g 2.3 1.62 5009.61 55.2 41.15 TS720, 20.0 g 2.4 2.16 800 9.99 56.4 54.86 Water 2.53.02 350 13.46 63.8 76.71 40.0 g Bay 3.1 0.99 50 5.28 30.1 25.15140/700T Clear 3.2 1.41 5.88 31.6 35.81 (60/40), 8.0 g 3.3 2.26 300 9.8254.4 57.40 TS720, 20.0 g 3.4 2.12 300 10.11 59.8 53.85 Water 3.5 2.14200 13.43 57.5 54.36

Example 4: One-Step Coating with BAYHYDROL®/Polane® Binder with VaryingAmounts of Second Particles and Thermoplastic First Particles (TigerDrylac)

The mixtures in Example 3 were duplicated with the exception that in allcases a 7% addition of a thermoplastic first particle powder (TigerDrylac) was added. Mixtures with each level of CAB-O-SIL® TS720 and 7%of first particle were sprayed, using an air spray gun, on five 4×4-in.square plates to achieve five different thicknesses on different plates.Each plate was subjected to thickness, surface roughness, and Taberabrasion testing, which is summarized in Table 6, and plotted in FIGS.9-1.1.

TABLE 6 Summary of Data for One-Step Coating on Steel Plates made withBAYHYDROL ® 140AQ and Clear 700T Fumed Silica TS720 was Varied from11-20% and 7% of Tiger Drylac was added as a First particle Number ofCoating Thick- Tabers Thick- ness 250-g R_(a) R_(z) ness Coating Plate #(mils) Load (μm) (μm) (μm) 40.0 g Bay 4.1 1.66 100 3.71 24.1 42.16140/700T Clear 4.2 1.89 5.61 33.7 48.01 (60/40), 4.4 g 4.3 2.18 300 6.3539.2 55.37 TS720, 2.8 Tiger 4.4 3.08 10.97 61.7 78.23 Drylac, 20.0 g 4.53.28 600 17.64 88 83.31 40.0 g Bay 5.1 1.31 500 9.47 53.2 33.27 140/700TClear 5.2 1.92 900 12.54 75.8 48.77 (60/40), 6.0 g 5.3 2.3 15.26 69.958.42 TS720, 2.8 Tiger 5.4 3.38 17.26 90.3 85.85 Drylac, 20.0 g 5.5 3.4810.85 54.4 88.39 40.0 g Bay 6.1 0.84 150 7.49 40.3 21.34 140/700T Clear6.2 1.13 300 8.09 46.4 28.70 (60/40), 8.0 g 6.3 1.63 700 10.04 56.741.40 TS720, 2.8 Tiger 6.4 2.06 1,000 10.50 58.9 52.32 Drylac, 20.0 g6.5 2.98 19.52 85.6 75.69 “Bay” = BAYHYDROL ® 20.0 g is 20 grams ofwater

Example 5: One-Step Coating with Binders Prepared with BAYHYDROL® 140AQand Polane® 700T White, and Three Levels of TS720 Ranging from 11-20%

The mixtures in Example 3 were duplicated with the exception that in allcases the clear POLANE® 700T was replaced with white POLANE® 700T(product F63W522). White 700T has about 15% TiO₂ pigment firstparticles. Data for this study on 4×4-in, steel plates are summarized inTable 7 and plotted in FIGS. 12-14.

A separation of surface roughness values is noted for compositions withwhite TS720 as opposed to clear TS720, which is used in Example 3 (seee.g., the Taber Abrader data, 13). As noted in Table 7, the coating for20% TS720 and 8 μm of PUD mixture cracked for all thicknesses;therefore, no Taber data were obtained. Data for TS720 of 11% show avery nice linear increase with increasing coating thickness. There wereonly two Taber data points for TS720 of 15%. One was higher and theother was much lower than TS720 of 11%.

TABLE 7 Summary of Data for One-Step Coating on Steel Plates made withBAYHYDROL ® 140AQ and White 700T. Fumed Silica TS720 Varied from 11-Number of Coating Thickness Tabers R_(a) R_(z) Thickness Coating Plate #(mils) 250-g Load (μm) (μm) (μm) 40.0 g Bay 7.1 0.88 400 5.43 37.9 22.35140/700T White 7.2 1.56 850 9.06 50.2 39.62 (60/40), 4.4 g 7.3 1.89 12009.37 53.9 48.01 TS720, 20.0 g 7.4 3.06 1200 14.02 77.6 77.72 Water 7.53.16 1900 11.60 60 80.26 40.0 g Bay 8.1 0.9 1.00 7.42 22.86 140/700TWhite 8.2 1.1 1.77 13.9 27.94 (60/40), 6.0 g 8.3 1.81 1.96 15.6 45.97TS720, 20.0 g 8.4 2.03 100 2.36 19.1 51.56 Water 8.5 2.16 1600 2.71 21.754.86 40.0 g Bay 9.1 0.74 Coating cracked 4.08 27.4 18.80 140/700T White9.2 1.32 Coating cracked 4.50 30.2 33.53 (60/40), 8.0 g 9.3 1.68 Coatingcracked 3.18 24 42.67 TS720, 20.0 g 9.4 2.04 Coating cracked 5.65 35.451.82 Water 9.5 2.4 Coating cracked 6.40 40.1 60.96

Example 6: One-step Coating with Binders of BAYHYDROL® 140AQ and Polane®700T and Three Levels of CAB-O-SIL® T5720 Ranging from 11-20%, and A 7%with Drylac First Particle Additions

The mixtures in Example 5 were duplicated with the exception that in allcases a 7% addition of a thermoplastic first particle powder (TigerDrylac) was added. Data for steel plates coated with these mixtures isgiven in Table 8 and plotted in FIGS. 15-17. Surface roughness valuesR_(a) and R_(z) show very similar trends (see FIGS. 15 and 16). TheR_(a) and R_(z) values increase linearly with increasing coatingthickness for all CAB-O-SIL® TS720 levels. Higher roughness values werenoted for CAB-O-SIL® TS720 of 11 and 15%. The lowest values were notedfor 20%. Abrasion resistance, measured as Taber abrasion cycles, showsan essentially linear increase with increasing thickness (see FIG. 17).Higher values were noted for CAB-O-SIL® TS720 of 11 and 15% as comparedto TS720 of 20%.

TABLE 8 Summary of Data for One-Step Coating on Steel Plates made withBAYHYDROL ® 140AQ and White 700. Fumed Silica TS720 Varied from 11-20%,and 7% of Tiger Drylac was added as First particle. Number of CoatingThickness Tabers R_(a) R_(z) Thickness Coating Plate # (mils) 250-g Load(μm) (μm) (μm) 40.0 g Bay 10.1 1.28 400 6.94 36.8 32.51 140/700T White10.2 1.84 1000 8.53 51.8 46.74 (60/40), 4.4 g 10.3 2 8.90 49.4 50.80TS720, 2.8 Tiger 10.4 2.36 600 12.70 62.8 59.94 Drylac, 20.0 g 10.5 2.76900 12.97 63.1 70.10 40.0 g Bay 11.1 1.05 250 5.37 32.9 26.67 140/700TWhite 11.2 1.24 6.69 42.3 31.50 (60/40), 6.0 g 11.3 1.68 500 7.58 41.242.67 TS720, 2.8 Tiger 11.4 2.05 900 11.71 59.3 52.07 Drylac, 20.0 g11.5 2.5 900 11.90 58.1 63.50 40.0 g Bay 12.1 0.92 100 4.16 24.9 23.37140/700T White 12.2 1.19 100 4.20 25.7 30.23 (60/40), 8.0 g 12.3 1.54400 4.32 29.3 39.12 TS720, 2.8 Tiger 12.4 1.738 3.54 23.2 44.15 Drylac,20.0 g 12.5 2.28 600 4.85 30.6 57.91

Example 7: Coatings with Varying TS720 Second Particle Content (from5-9%) without First Particle Additions

Taber abrasion durability and surface roughness data were obtained fortwo sets of steel plates, coated with two compositions differing only inthe binder component of the coating. One composition was prepared with abinder of 60:40 BAYHYDROL® 140AQ and clear POLANE® 700T (productF63V521) (v/v) and the other coated with a binder of 60:40 BAYHYDROL®140AQ and white POLANE® 700T (product F63W522) (v/v). With both binders,CAB-O-SIL® TS 720 content was varied from 5 to 9% (w/w based on theweight of the binder composition). Three different thicknesses of eachTS720-containing composition were spray-coated on steel plates andprocessed identically as in the preceding examples. After curing, allplates were subjected to measurement of coating thickness, surfaceroughness, and testing of resistance of the coatings' resistance to theloss of their hydrophobidoleophobic properties using a Taber abrader(250 g load and CS10 wheels) Data for clear 700T plates is summarized inTable 9 and for white 700T in Table 10.

TABLE 9 Summary of Data for One-Step Coating on Steel Plates made withBAYHYDROL ® 140AQ and Clear 700T. Fumed Silica TS720 Varied from 5-9%(Without First Particle Additions) Number of Coating Thick- TabersThick- ness 250-g R_(a) R_(z) ness Coating Plate # (mils) Load (μm) (μm)(μm) 40.0 g Bay 1.1 0.82 10 1.66 10.73 20.83 140/700T Clear 1.2 1.16 103.88 22.13 29.46 (60/40), 2.0 g 1.3 1.5 10 3.16 16.47 38.10 TS720, 3 gWater 40.0 g Bay 2.1 0.62 10 1.67 12.93 15.75 140/700T Clear 2.2 1.4 301.78 12.73 35.56 (60/40), 2.8 g 2.3 1.63 30 1.61 14.07 41.40 TS720, 4 gWater 40.0 g Bay 3.1 0.72 120 2.37 16.53 18.29 140/700T Clear 3.2 1.34130 2.50 17.03 34.04 (60/40), 3.6 g 3.3 1.69 160 2.93 19.68 42.93 TS720,6 g Water

TABLE 10 Data for One-Step Coatings on Steel Plates Made withBAYHYDROL ® 140AQ and White 700T Binder and Cab-O-Sil TS720 from 5%-9%Number of Coating Thick- Tabers Thick- ness 250-g R_(a) R_(z) nessCoating Plate # (mils) Load (μm) (μm) (μm) 40.0 g Bay 4.1 0.55 10 3.1618.37 13.97 140/700T White 4.2 0.88 15 6.76 38.60 22.35 (60/40), 2.0 g4.3 1.04 75 6.42 37.03 26.42 TS720, 3 g Water 40.0 g Bay 5.1 0.41 403.35 19.80 10.41 140/700T White 5.2 1.09 80 3.30 22.73 27.69 (60/40),2.8 g 5.3 1.48 100 3.24 22.07 37.59 TS720, 8.8 g Water 40.0 g Bay 6.10.44 80 4.33 23.73 11.18 140/700T White 6.2 0.79 300 6.67 35.77 20.07(60/40), 3.6 g 6.3 1.59 400 12.68 55.30 40.39 TS720, 15 g Water

Plots for the abrasion resistance vs. coating thickness obtained withbinder that employed clear POLANE® 700T (FIG. 18) showed increasingdurability with increasing coating thickness and increasing TS720 from5-9%. The slope of the Taber durability data, however, is low for TS720at 5% relative to larger slopes observed with higher levels of TS720content. When CabO-Sil TS720 content increases to 11%, the slope ofabrasion resistance vs. coating thickness plots increases sharply (see,e.g., FIG. 20). For white POLANE® 700T with titanium dioxide pigmentthird particles (white, FIG. 19), the observed change in slope withincreasing coating thickness followed a similar trend to that observedwith clear POLANE® 700T, but the actual slopes are greater than withclear POLANE® 700T.

Increases in the slope of the abrasion resistance vs. coating thicknessplots again suggests that the second particles (e.g., TS720 particles)are distributed uniformly throughout the coating thickness (see e.g.,FIG. 2), and the Taber cycles increase as abrasion does not simplyremove the majority of second particles when the surface is abraded.Surface abrasion exposes more material with second particles resultingin the continued hydrophobicity and/or oleophobicity of the newlyexposed surface. The physical manifestation of this aspect is that theend of superhydrophobicity occurs when coating wears through (e.g., downto bare metal or an underlying coating layer), not when its surface isabraded away. At TS720 concentrations less than 11%, the slopes of thelines representing a correlation between abrasion resistance and coatingthickness, suggest the TS720 particles may be concentrated to a greaterdegree at the outside (the exposed surface of the coating that forms aninterface with air). Thus, as the exposed surface wears out, thesuperhydrophMicity, is more quickly lost.

Surface roughness (Tables 9 and 10) for the samples in this example,suggest that TS720 content of about 11% with white POLANE® 700T provideshighly durable SH and/or OP coatings that display thickness dependentabrasion resistance. Where smoother surfaces finishes are desired, clearPOLANE® 700T can be employed to achieve highly durable S and/or OPcoatings that display thickness dependent abrasion resistance

Surface Roughness Data

The surface roughness data for all four coatings with a fixed TS720content of 11% are shown in FIGS. 26-28. FIG. 26 shows that whitePOLANE® 700T results in more surface roughness with or without firstparticle than clear POLANE® 700T. FIG. 27 shows the difference betweencoating formed with clear and white POLANE® compositions without firstparticle additions. For a coating thickness of 50 μm, the surfaceroughness of the coatings with white 700T is ˜1.3× that of clear 700T.

Data in FIG. 28 compared the surface roughness with first particlebetween white 700T and clear 700T. Again, for a coating thickness of 50μm, the white 700T results in a factor of ˜1.6×. Thus, if surfaceroughness is critical, the 60:40 BAYHYDROL® 140AQ should be blended withclear 700T.

Example 8: Top Coating of One-Step Coatings Made with BAYHYDROL® 140AQto Achieve Enhanced Oleophobic Performance

Aluminum plates, 4×4-inch, were base-coated with a composition preparedby mixing:

-   -   1. 60:40 mixture of BAYHYDROL® 140AQ: clear POLANE® 700T by        volume as the binder;    -   2. 7% (by weight of hinder) Tiger Dry-lac clear matte first        particle;    -   3. 11% (by weight) TS720; and.    -   4. 50% (by weight) water.    -   After drying or approximately 30 min at room temperature in        ambient humidity, the base coat was top coated with either top        coat composition No. 1 or No. 2.    -   Top Coat No. Top coat composition No. I consisted of 1% M5        (untreated fumed silica), 0.5% SiCl₄, and 0.5% (Gelest 8174)        (tridecafluoro-1,1,2,2-tetrahyrctyltrichlorsilane). The top        coated plate was cured for 1 h at 200° F. The top coated plate        was SH and OP. It lasted 5 min under a shower and demonstrated        an abrasion resistance of 600 Taber cycles at a 250 g load with        CS1.0 wheels    -   Top Coat No. 2: Top coat composition No. 2 employed the same        component composition as top coat No. 1, with the exceptions        that the M5 silica content was increased from 1 to 2% and the        silane content was increased from 0.5 to 1%. The plate top        coated with composition No. 2 was cured for 1 h at 200° F. This        plate lasted 5-10 min under a shower and demonstrated an        abrasion resistance of 900 Taber cycles at a 250 g load with        CS10 wheels.    -   Shower Test: A measure of the durability of superhydrophobicity        can be made by measuring time exposure to a constant water        shower which is required to wet a specimen. This equipment        consists of a shower spray head positioned 6 feet above the        sample through which a full flow of water is delivered from        normal facility water supply.

Example 9: A One-Step Coating Composition Yielding Superhydrophobic andOleophobic Coatings

A coating composition comprising:

-   -   BAYHYDROL®124-24.0 grams    -   POLANE® 700T (white)-16.0 grams    -   M5T=9.0 grams (Cab-o-Sil M5 silica treated with        (3,3,4,4,5,5,6,6,6-Nonafluorohexyl)trichlorosilane (SIN 6597.6)        as described below)    -   Corvel Black—2.8 grams and    -   H₂O—20.0 grams        was prepared by blending the components as follows:

BAYHYDROL® 124 (24.0 grams) and POLANE® 700T (16.0 grams) were blendedtogether for 20 minutes. The addition of MST (9.0 grams, M5 silicatreated with (3,3,4,4,5,5,6,6,6-Nonafluorohexyl)trichlorosilane (SIN6597.6)) to the solution was followed by mixing in a ball mill for 30minutes. Addition of Corvel Black (2.8 grams) and H₂O (20.0 grams) tothe solution was followed by an additional 30 minutes of mixing in aball mill.

The coating was applied using a Central Pneumatic spray gun with thenozzle size of 0.020-0.025 inches. A coating thickness of 1.2-1.4 milswas applied to a 4×4 inch Al-plate. The plate was cured at roomtemperature for 30 minutes followed by curing at 200F for 1-2 hours.After curing, the plates were tested for superhydrophobicity,oleophobicity, Taber abrasion resistance, and shower resistance to lossof superhydrophobicity. The results of the tests show the coatingdisplays superhydrophobicity (contact angle=167.33, after Taber abrasiontesting=(155.23). The coatings also display oleophobic/superoleophobicbehavior (contact angle=153.67). The coating lost itssuperhydrophobicity after 500 Taber abrasion cycles with a 250 gramload. Superhydrophobicity is lost after 55-60 minutes in shower testing(described above); however, superhydrophobicity returns after drying.

Example 10: Volatile Organic Compounds (VOCS) Content of Coatings withBAYHYDROL® 140AQ

Of the binder components employed in this disclosure, BAYHYDROL® 140AQemployed more volatile organic solvent (toluene) than any othercomponent. As it is desirable for environmental reasons to reduce theVOC contents of products, including those employed in making SH and OPcoatings, an analysis of the expected VOC content of exemplary coatingcomposition components is set forth for reference. The calculated VOCcontent, based on ingredients for various coatings/coating components,is set forth in Table 11.

TABLE 11 Volatile Organic Compound Values for Select Coatings (MinusWater and Exempt Solvents) Approximate VOC Content CoatingComponent/Compositions (pounds per gallon) Composition 1: 0.3 60:40BAYHYDROL ® 140AQ: clear/white POLANE ® 700T, 9-20% TS720 secondparticles, 0-7% first particle Corvel Black or Tiger Drylac) Composition2: 0 0.5-1% Fluorinated silanizing agent, 0.5% SiCl4, .1-2% M5, balanceAcetone Composition 3: 4.7 POLANE ® B component 2.2 POLANE ® Acomponents Composition 4: 5.4 5-1% Fluorinated silane, 0.5% SiCl4, 1-3%M5, balance Hexane

It can be seen from Table 11 that Composition 1, which is a BAYHYDROL®140AQ-based coating, has approximately 0.3 lb/gallon of VOCs. Thatcoating delivers SH behavior with a very significant abrasion resistancebased on Taber Abrader durability data with limited VOCs released in thecoating process. The application of a top coat top coat of Composition 2to the coating formed from Composition 1 adds no additional VOCs, butthe coating now also delivers the OP behavior in addition to hydrophobicbehavior. In contrast, coatings formed using solvent based POLANE® A andB (Composition 3), with a top coat (Composition 4) delivers excellentabrasion durability and wetting resistance but with a significantrelease of VOC compounds.

Example 11: A One-step Coating with Different Levels of TreatedCAB-O-SIL M5 Particles Treated with a Silanizing Agent

M5 silica particles treated withtridecafluorotetrahydrooctyltrichlorosilane were incorporated intobinder a binder composition and applied using different sprayingtechniques. The base composition consisted of:

-   -   BAYHYDROL® 124 (Bayer)=24.0 g    -   POLANE® 700T (with white pigment, Sherwin Williams)=16.0 g

(In some cases, as indicated, clear POLANE® 700T of the same amount wasused)

-   -   M5T (fumed silica particles treated with SIT 8174.0 (Gelest,        tridecafluorotetrahydrooctyltrichlorosilane)=4.4 g    -   Water=18.20 g

The treated particles were added to the BAYHYDROL® 124/700T mix to makea paste. The paste was diluted with water to achieve the consistency forspraying or painting. The composition was applied to 4×4-in. aluminumplates by using the following procedures: (All plates were tested forsurface roughness and resistance to SH and/or OP loss using Taberabrasion. The loss of oleophobicity with Taber abrasion was alsomeasured for each sample

Example 11: Part A

BAYHYDROL® 124/POLANE® 700T (White)—40.0 g

M5T (8174 Tridecafluorotetrahydrooctyltrichlorosilane)—4.4 g (11% w/w tothe binder)

H₂O—18.0-20.0 g

The composition was applied using an air spray gun with 1.4 mm nozzleand the surface of the plates to be coated placed vertically. Visualinspection of plates after curing (drying at 200° F.) showed sagging ofthe coating due to water running down the plate during application. Someof the areas of the coating were much lighter visually then other areasthat seemed to have proper coating coverage.

The plates were found to be superhydrophobic and superoleophobic.Roughness measures yielded an Ra values of 2.307, 1.392, 1.824, 1.842,and 1.679, and Rz values of 16.0, 11.0, 13.7, 12.7, and 11.7. Taberabrasion measurements using a 250 g load (CS10 wheels) gave values of200, with one sticky spot due to a thick coating area. Taber abrasionresistance for loss of superoleophobicity yielded a value of 3.5. Showerresistance to loss of superhydrophobicity greater than 1 hours with somewetting at 2 hours. Exposure to rain showed superhydrophobicity afterone hour of rain exposure outdoors.

Example 11: Part B

BAYHYDROL® 124/POLANE® 700T (White)—40.0 g

M5T (8174 Tridecafluorotetrahydrooctyltrichlorosilane)—4.4 g (11% w/w tothe Binder)

H₂O—18.0-20.0 g

The composition was applied using an air spray gun and the surface ofthe plates to be coated placed horizontally. Visual inspection of platesafter curing (drying at 200° F.) showed good coverage, smoothness, andsubstantially uniform coatings.

The plates were found to be superhydrophobic and superoleophobic.Roughness measures yielded an Ra values of 2.377, 2.386, 2.657, and1.679, and Rz values of 16.1, 17.0, 18.5, 12.7, and 11.7. Taber abrasionmeasurements using a 250 g load (CS10 wheels) gave values of 400-500abrasion cycles for superhydrophobicity. Taber abrasion resistance forloss of superoleophobicity yielded a value of 15 abrasion cycles. Showerresistance to loss of superhydrophobicity greater than 2 hours. Exposureto rain showed superhydrophobicity after one hour of rain exposureoutdoors.

Example 11: Part C

BAYHYDROL® 124/POLANE® 700T (White)—40.0 g

M5T (8174 Tridecafluorotetrahydrooctyltrichlorosilane)—4.4 g (11% w/w tothe Binder)

H₂O—18.0-20.0 g

The composition was applied using an air spray gun with small nozzle(600 micron opening) and the surface of the plates to be coated placedhorizontally Visual inspection of plates after curing (drying at 200°F.) showed good coverage and smoothness. The small nozzle is lesseffective at spraying a good uniform coating when simultaneouslyspraying multiple plates with a large area to be coated.

The plates were found to be superhydrophobic and superoleophobic.Roughness measures yielded Ra values of 2.903, 3.581, and 2.920 and Rzvalues of 16.5, 19.7, and 14.6. Taber abrasion measurements using a 250g load (CS10 wheels) gave values of 200 abrasion cycles, worn to baremetal. Taber abrasion resistance for loss of superoleophobicity yieldeda value of 10. Exposure to rain showed superhydrophobicity after onehour of rain exposure outdoors.

Example 11: Part D

BAYHYDROL® 124/POLANE® 700T (Clear)—40.0 g

MST (8174 Tridecafluorotetrahydrooctyltrichlorosilane)—4.4 g (11% w/w tothe Binder)

H₂O—18.0-20.0 g

Procedure: Small Gun with Plates Horizontal. Visual inspection of platesafter curing showed good coverage, very smooth, and high uniformity.

The composition was applied using an air spray gun with small nozzle(0.6 mm or 600 micron opening) and the surface of the plates to becoated placed horizontally Visual inspection of plates after curing(drying at 200° F.) showed good coverage, a very smooth finish, and highuniformity over the surface.

The plates were found to be superhydrophobic and superoleophobic.Roughness measures yielded Ra values 0.847, 0.840, and 1.143 microns,and Rz values of 6.46, 6.50, and 9.17 microns. Taber abrasionmeasurements using a 250 g load (CS10 wheels) gave values of 300abrasion cycles. Taber abrasion resistance for loss ofsuperoleophobicity yielded a value of 5 abrasion cycles. Exposure torain showed superhydrophobicity after one hour of rain exposureoutdoors.

Example 11: Part E

BAYHYDROL® 124/POLANE® 700T (Clear)—60.0 g

M5T (8174 Tridecafluorotetrahydrooctyltrichlorosilane)—5.3 g (8.8% w/wto the binder)

H₂O—10.0 g

The composition was applied using an air spray gun with small nozzle(0.6 mm or 600 micron opening) and the surface of the plates to becoated placed horizontally Visual inspection of plates after curing(drying at 200° F.) showed good coverage, a very smooth finish, and highuniformity over the surface.

The plates were found to be superhydrophobic and superoleophobic.Roughness measures yielded Ra values 1.310, 0.997 microns, and 1.266,and Rz values of 10.2, 7.34, and 9.79 microns. Taber abrasionmeasurements using a 250 g load (CS10 wheels) gave values of 400abrasion cycles. Taber abrasion resistance for loss ofsuperoleophobicity yielded a value of 5 abrasion cycles. Exposure torain showed superhydrophobicity after one hour of rain exposureoutdoors.

Example 11: Part F

BAYHYDROL®124/POLANE® 700T (Clear)—60.0 g

MST (8174 Tridecafluorotetrahydrooctyltrichlorosilane)—4.4 g (7.3% w/wto the Urethane)

H₂O—10.0 g

The composition was applied using an air spray gun with small nozzle(0.6 mm or 600 micron opening) and the surface of the plates to becoated placed horizontally Visual inspection of plates after curing(drying at 200° F.) showed good coverage, a very smooth finish, and highuniformity over the surface.

The plates were found to be superhydrophobic and superoleophobic.Roughness measures yielded Ra values 0.777, 0.643, and 0.607 microns,and Rz values of 8.44, 6.53, and 5.50 micron. Taber abrasionmeasurements using a 250 g load (CS10 wheels) gave values of 300abrasion cycles. Taber abrasion resistance for loss ofsuperoleophobicity yielded a value of 5 abrasion cycles. Exposure torain showed superhydrophobicity after one hour of rain exposureoutdoors.

TABLE 12 Summary of Data for Example 11 Taber Taber Cycles Cycles Show-Surface for End for End er Coating Spray Roughness of of SO TimeComposition Gun Ra(micron) SH (#) (#) (h) 124/700T(W) = 40 g Large Gun1.81 200 4 2 M5T (8174) = 4.4 g Plate Water = 18-20 g Vertical124/700T(W) = 40 g Large Gun 2.47 450 15 2 M5T (8174) = 4.4 g PlateWater = 18-20 g Horizontal 124/700T(W) = 40 g Small Gun 3.13 200 10 M5T(8174) = 4.4 g Plate Water = 18-20 g Horizontal 124/700T(C) = 40 g SmallGun 0.943 300 5 M5T (8174) = 4.4 g Plate Water = 18-20 g Horizontal124/700T(C) = 40 g Small Gun 1.191 400 5 M5T (8174) = 3.53 g Plate Water= 6.67 g Horizontal 124/700T(C) = 40 g Small Gun 0.675 300 5 M5T (8174)= 2.93 g Plate Water = 6.67 g Horizontal

Example 12: A One-Step Coatings with Glass Bead First Particle Addition

To the compositions of Example 11 was added 7% (by weight of the binder)of glass bubbles (S60, from 3M Company, see Table 1). Coatings withoutfirst particles added were prepared with clear POLANE 700T and thosewith S60 were Prepared with white POLANE 700T. The coatings were appliedon 4×4 inch steel plates with gun using four different nozzle sizes tocreate different coating thicknesses. All of the plates were cured at200° F. for 1 hour (h) after which coating thickness was measured andTaber abrasion wear resistance to the point where they lostsuperhydrophobicity assessed. The Taber testing was conducted at threedifferent loads (250, 500, and 1000 g). All of the Taber data andcoating thickness (in mils and microns) are summarized in Table 13 andTable 13A.

TABLE 13 Taber Data for Example 11 for Various Thicknesses at Loads of250, 500, and 1000 g Plate Thickness Taber System # (mil) Tabers Load(g) microns 60/40 Bay 124/700T clear 1 1.30 300 250 33.02 (NoFiller)-1.3 nozzle 2 1.28 200 500 32.512 3 1.08 150 1000 27.432 60/40Bay 124/700T white 4 2.28 800 250 57.912 (7% S60)-1.3 nozzle 5 1.84 425500 46.736 6 2.22 175 1000 56.388 60/40 Bay 124/700T clear 7 2.84 200250 72.136 (No Filler)-1.5 nozzle 8 2.16 150 500 54.864 9 1.96 400 100049.784 60/40 Bay 124/700T white 10 2.54 1650 250 64.516 (7% S60)-1.5nozzle 11 2.38 700 500 60.452 12 2.90 175 1000 73.66 60/40 Bay 124/700Tclear 13 1.78 300 250 45.212 (No Filler)-1.8 nozzle 14 2.46 150 50062.484 15 2.04 575 1000 51.816 60/40 Bay 124/700T white 16 3.22 2550 25081.788 (7% S60)-1.8 nozzle 17 3.18 850 500 80.772 18 3.44 200 100087.376 60/40 Bay 124/700T clear 19 2.24 350 250 56.896 (No Filler)-2.2nozzle 20 2.64 350 500 67.056 21 3.06 800 1000 77.724 60/40 Bay 124/700Twhite 22 3.78 2500 250 96.012 (7% S60)-2.2 nozzle 23 4.92 1525 500124.968 24 4.54 425 1000 115.316

Four additional plates were coated to create coatings thicker than thoseappearing in Table 13. The coatings on the additional plates range inthickness from 4 to 12 mils. Data for this study are presented in Table13A and included in FIG. 32.

TABLE 13A Taber Data for Very Thick Coatings using 1000-g Load TaberThick- Load System Plate # ness Tabers (g) Microns 60/40 BAYHYDROL 2512.1 1400 1000 307.34 124/White POLANE 26 8.18 1000 1000 207.772 700T(7% S60) small 27 6.40 800 1000 162.56 gun 28 4.24 400 1000 107.669

Data from Table 13 and Table 13A are plotted in FIGS. 29-32. Those plotsshow Taber abrasion resistance data for each applied load (250, 500, and1000 g).

The invention claimed is:
 1. A coating composition for the applicationof superhydrophobic, or superhydrophobic and oleophobic, coatings onsurfaces comprising: a one-component waterborne polyurethane dispersionor suspension comprising one or more of a polyester urethane, apolyacrylic urethane and/or a polycarbonate urethane in water, or awater containing medium; about 5 to about 30% by weight of hydrophobic,or superhydrophobic and oleophobic, second particles comprising one ormore siloxanes, and/or one or more alkyl, haloalkyl, fluoroalkyl, orperfluoroalkyl containing moieties; said composition optionallycomprising up to about 26% by weight of third particles; wherein saidcoating composition comprises less than 0.3 pounds per gallon ofvolatile non-exempt organic compounds; wherein said coating compositionoptionally comprises first particles; and wherein the superhydrophobiccoating resulting from the application of said composition to a surfaceretains its superhydrophobicity after 150-1,400 Taber abrasion cycles ata 1000 g load for a coating thickness range of 25-300 microns, and/or100-2,500 Taber abrasion cycles at a 250 g load, using a CS10 wheel, asjudged by the inability of more than 50% of the water droplets appliedto the area of the coating subjected to said abrasion cycles to remainon the surface when the planar surface is inclined at 3 degrees.
 2. Thecomposition of claim 1, wherein said composition does not comprise firstparticles and the superhydrophobic coating resulting from theapplication of said composition to a planar surface retains itssuperhydrophobicity after 150-800 Taber abrasion cycles at a 1,000 gload, for a thickness range of 25-75 microns, and/or 200-1,400 Taberabrasion cycles at a 250 g load for a thickness range of 25-75 microns,on a planar surface using a CS10 wheel, as judged by the inability ofmore than 50% of the water droplets applied to the area of the coatingsubjected to said abrasion cycles to remain on the surface when theplanar surface is inclined at an angle of 3 degrees.
 3. The compositionof claim 1, wherein said composition further comprises first particles.4. The composition of claim 3, wherein the first particles are selectedfrom oxides of metalloids, metal oxides, one or more thermoplastics, oneor more thermoset plastics, one or more metals, one or more glasses,and/or one or more hollow spheres.
 5. The composition of claim 3,wherein the superhydrophobic coating resulting from the application ofsaid composition to a planar surface retains its superhydrophobicityafter 100-600 Taber abrasion cycles at a 250 g load for a thicknessrange of 40-85 microns using a CS10 wheel, as judged by the inability ofmore than 50% of the water droplets applied to the area of the coatingsubjected to said abrasion cycles to remain on the surface when theplanar surface is inclined at an angle of 3 degrees.
 6. The compositionof claim 1, wherein said polyurethane suspension or dispersion comprisesthird particles.
 7. The composition of claim 1, wherein the compositioncomprises a mixture of polyacrylic urethanes and polycarbonateurethanes.
 8. The composition of claim 1, wherein said one or morealkyl, haloalkyl, fluoroalkyl, or perfluoroalkyl containing moieties areone or more alkylsilane and/or fluoroalkylsilane groups.
 9. Thecomposition of claim 8, wherein said alkylsilane and/orfluoroalkylsilane groups result from the reaction of silica or metaloxide particles with one or more silanes selected from the groupconsisting of: a compound of formula I;(tridecafluoro-1,1,2,2-tetrahydrooctyl)silane;(tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane;(tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane;(tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane;(heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethyl(dimethylamino)silane;(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tris(dimethylamino)silane;n-octadecyltrimethoxysilane; n-octyltriethoxysilane; and3,3,4,4,5,5,6,6,6-nonafluorohexyldimethyl(dimethylamino)silane.
 10. Thecomposition of claim 9, wherein said second particles are present fromabout 20% to about 30% by weight.
 11. The composition of claim 9,wherein said coating is both superhydrophobic and oleophobic.
 12. Thecomposition of claim 1, that when dried and cured produces a surfacewith an arithmetic mean roughness (Ra) of less than about 20 microns.13. The composition of claim 1, comprising from about 30% to about 50%polyurethanes by weight.
 14. The composition of claim 1, wherein saidpolyurethane dispersion or suspension comprises at least one polyesterurethane, polyacrylic urethane, and/or polycarbonate urethanecomposition that when dried and cured produces a coating that has: (a) amodulus at 100% elongation of 1300 psi or greater, and/or (b) anelongation percent at break of 150% or greater.
 15. The composition ofclaim 1, further comprising 0.1-10, 10-20, 20-30, 30-40, 40-50 or 50-60g of one or more compatible solvents per 100 g of coating composition.16. The composition of claim 15, wherein said one or more compatiblesolvents are VOC-exempt solvents, and wherein said coating compositioncomprises less than 0.3 pounds per gallon of volatile non-exempt organiccompounds.
 17. The composition according to claim 16, wherein said oneor more VOC-exempt solvents comprise water.
 18. A superhydrophobicand/or oleophobic coating formed by the application of the compositionof claim
 1. 19. The coating of claim 18, wherein said coating formed ona flat flexible surface can withstand being bent to a right angle arounda ¼ inch cylinder greater than about 100 times without loss ofhydrophobicity or oleophobicity.
 20. A method of coating at least partof a surface comprising the application of a composition of claim 1.